Alicyclic diamines, alicyclic diisocyanates and polyisocyanato-isocyanurates and method for the preparation thereof

ABSTRACT

Herein disclosed are an α-(aminocyclohexyl)alkylamine represented by the following general formula (II): ##STR1## wherein R represents hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms, provided that the amino group bonded to the cyclohexyl group may be in either of the 2-, 3- and 4-positions and a method for preparing it; an α-(isocyanatocyclohexyl)alkylisocyanate of Formula (II) wherein the amino groups are replaced with isocyanato groups and a method for preparing it; polyisocyanato-isocyanurate represented by the following general formula (IV): ##STR2## wherein R 1 , R 2  and R 3  may be the same or different and each represents a group represented by the following general formula: ##STR3## wherein R represents hydrogen atom or an alkyl group having 1 to 5 carbon atoms and n is an integer ranging from 1 to 5 and a method for preparing it; and a resin obtained by polymerizing an organic polyisocyanate containing not lower than 10% by weight of the polyisocyanato-isocyanurate represented by Formula (IV) and a compound having at least two active hydrogen atoms as well as a resin composition for coating materials which comprises the resin.

This application is a divisional of application Ser. No. 07/866,551,filed Apr. 10, 1992, issued May 11, 1993 as U.S. Pat. No. 5,210,286,which is a divisional application of application Ser. No. 07/511,183,filed Apr. 19, 1990, issued June 30, 1992 as U.S. Pat. No. 5,126,426.

BACKGROUND OF THE INVENTION

1) Field of the Invention

The present invention relates to alicyclic diamines, alicyclicdiisocyanates and polyisocyanato-isocyanurates as well as a method forthe preparation of these compounds and the use thereof as isocyanatecomponents. The alicyclic diamines, alicyclic diisocyanates andpolyisocyanato-isocyanurates are each compounds having a novel structureand the alicyclic diamines can be used as hardening agents for epoxyresins, polyurethanes and polyureas as well as starting materials forpreparing polyamides. The alicyclic diisocyanates can widely be used invarious fields, for instance, in expandable materials, elasticmaterials, synthetic leathers, coating materials, adhesives, films andfibers as well as starting materials for polyurethane resins, polyurearesins and polyamides. Moreover, the polyisocyanato-isocyanurates can beused as expandable materials, adhesives and resins for coating materialsas well as starting materials therefor.

2) Description of the Prior Art

An example of alicyclic diamines which have conventionally beenwell-known is bis(aminomethyl)cyclohexane (hereinafter refereed to as"H₆ -XDA") represented by the following formula (a): ##STR4## Thiscompound has widely been employed in various fields as a startingmaterial for epoxy resins and polyamides,

An example of alicyclic diisocyanates which have conventionally beenwell-known is bis(isocyanatomethyl)cyclohexane represented by thefollowing formula(b)(hereinafter referred to as "H₆ -XDI"): ##STR5##This compound has widely been used in various fields as a startingmaterial for polyurea resins and the like.

In addition, an example of Polyisocyanato-isocyanurates which haveconventionally been well-known is an isocyanurate of hexamethylenediisocyanate represented by the following formula (c): ##STR6## This hasbeen widely used in various fields as a resin for two-pack urethanecoating materials as well as a starting material for the resin.

Saunders Frisch (High Polymers, Vol. XVI, "Polyurethanes: Chemistry andTechnology II, Technology", p. 453) ptoposes resins which comprise, aschief materials, alkyd resins, polyester polyols, acryl polyols or epoxypolyols and, as a hardening agent, an urethane type polyisocyanatederived from tolylene diisocyanate or an isocyanurate typepolyisocyanate, as typical examples of the most general-purpose resinsfor two-pack urethane coating materials. These resins have been used notonly in coating materials for furniture and woodworking, but also incoating materials for heavy duty anticorrosion so-called tar-urethanepaints. However, urethane coating materials obtained from tolylenediisocyanate show substantially low weatherability.

In order to enhance the weatherability of these resins for coatingmaterials, there have been proposed the use of urethane typepolyisocyanates derived from hexamethylene diisocyanate (HDI) (see, forinstance, Japanese Patent Publication for Opposition Purpose (hereunderreferre to as "J.P. KOKOKU") No. Sho 45-11146); biuret typepolyisocyanates (see, for instance, U.S. Pat. No. 3,903,127);isocyanurate type polyisocyanates (see, for instance, U.S. Pat. Nos.3,487,080, 4,324,879 and 4,412,073); urethane-modified isocyanurate typeurethane isocyanates (see, for instance, Japanese Patent Un-examinedPublication (hereunder referred to as "J.P. KOKAI") No. Sho 57-47321 andU.S. Pat. No. 4,582,888). Specific examples of biuret typepolyisocyanates are OLESTER NP100 (available from MITSUI TOATSUCHEMICALS, INC.) and Desmodur N-75 (available from Sumitomo Bayer Co.,Ltd.); specific examples of HDI isocyanurate type polyisocyanates areSumidur N-3500 (available from Sumitomo Bayer Co., Ltd.) and CORONATE EH(available from NIPPON POLYURETHANE CO., LTD.). Organic polyisocyanatesderived from an aliphatic or alicyclic compound such as isophoronediisocyanate (IPDI) or 4,4'-dicyclohexylmethane diisocyanate are known.

Specific examples of isocyanurate type polyisocyanates of IPDI includeIPDI-T1890 (available from DAICEL-HUELS LTD.); examples of IPDIurethane-modified polyisocyanates are IPDI-UT647 and IPDI-UT-880(available from DAICEL-HUELS LTD.). There have been used two-packurethane coating materials which comprise these hardening agents andacryl polyols or polyester polyols as chief components.

These two-pack urethane coating materials are excellent in variousproperties such as weatherability, flexibility and wear resistance andsecure an immovable position in, for instance, the repair of automobilesand facing of buildings and structures. However, they show insufficientdrying characteristics. Therefore, they must be baked at a hightemperature or must be allowed to stand for a long time period to obtainwell-crosslinked tough coating material films therefrom.

As has been described above, conventional resins for two-pack urethanepaints suffer from various drawbacks. For instance, tolylenediisocyanate type resins have high reactivity and hence are excellent indrying characteristics, but show substantially low weatherability, whilealiphatic or alicyclic type resins are excellent in weatherability, buthave unsatisfactory drying characteristics.

Thus, it has long been desired to develop two-pack urethane coatingmaterials excellent in both weatherability and drying characteristics.

SUMMARY OF THE INVENTION

Accordingly, a first object of the present invention is to provide anovel alicyclic diamine which has a structure quite different from thatof H₆ -XDA and is expected to be a novel starting material for epoxyresins and polyamide resins.

A second object of the present invention is to provide a novel methodfor preparing the foregoing alicyclic diamine.

The alicyclic diamines according to the present invention arerepresented by the following general formula (II): ##STR7## (wherein Rrepresents a hydrogen atom or a lower alkyl group having 1 to 5 carbonatoms and the amino group attached to the cyclohexyl group may be ineither of the 2-, 3- and 4-positions) and can be prepared by the methodof this invention which comprises catalytically reducing aromaticdiamines represented by the following general formula (I): ##STR8##(wherein R is the same as that defined above and the amino groupattached to the phenyl group may be in either of the 2-, 3- and4-positions) in the presence of a ruthenium catalyst, water and analkali or alkaline earth metal hydroxide.

In this respect, α-(aminocyclohexyl)alkylamines represented by thefollowing general formula (II') and α-(3-aminocyclohexyl) ethylaminerepresented by the following formula (II') are novel compounds: ##STR9##wherein R' represents a lower alkyl group having 2 to 5 carbon atoms andthe amino group attached to the cyclohexyl group may be in either of the2-, 3- and 4-positions.

A third object of the present invention is to provide a novel alicyclicdiisocyanate which has a structure quite different from that of H₆ -XDIand is expected to be a novel starting material for resins such aspolyurethane resins and polyurea resins.

A forth object of the present invention is to provide a novel method forpreparing the foregoing diisocyanate.

The alicyclic diisocyanate of the present invention is represented bythe following general formula (III): ##STR10## (wherein R represents ahydrogen atom or a lower alkyl group having 1 to 5 carbon atoms and theisocyanato group attached to the cyclohexyl group may be in either ofthe 2-, 3- and 4-positions) and prepared by the method of this inventioncomprises reacting alicyclic diamines represented by the followinggeneral formula (II): ##STR11## (wherein R is the same as that definedabove in connection with the general formula (III)) or salts thereofwith phosgene.

A fifth object of the present invention is to provide a novelpolyisocyanato-isocyanurate which has a structure quite different fromthat of the resin represented by the formula (c) and is expected to be anovel resin for coating materials and a starting material therefor.

A sixth object of the present invention is to provide a novel method forpreparing the foregoing polyisocyanato-isocyanurate.

The polyisocyanato-isocyanurates of the present invention arerepresented by the following general formula (IV) ##STR12## wherein R₁,R₂ and R₃ may be the same or different and each represents a grouprepresented by the following general formula: ##STR13## (in the group, Rrepresents a hydrogen atom or a lower alkyl group) and n is an integerranging from 1 to 5; and prepared by the method of the invention whichcomprises trimerization of alicyclic diisocyanates represented byFormula (III) in the presence of an alkali metal compound of acarboxylic acid, an alkali metal compound of cyanic acid and optionallya polyethylene oxide compound or an alcohol.

A seventh object of the present invention is to provide an organicpolyisocyanate composition which comprises thepolyisocyanato-isocyanurate represented by the foregoing formula (IV) inan amount of not less than 10% by weight and less than 100% by weight,and a resin obtained by polymerizing the organic polyisocyanatecomposition with a compound having at least two active hydrogen atoms aswell as a resin composition for coating materials which comprises theaforementioned resin.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 is an IR chart observed on the α-(3-aminocyclohexyl) ethylamineobtained in Example 1;

FIG. 2 is an IR chart observed on theα-(3-isocyanatocyclohexyl)ethylisocyanate obtained in Example 7;

FIG. 3 is an NMR chart observed on theα-(3-isocyanatocyclohexyl)ethylisocyanate obtained in Example 7; and

FIG. 4 is an IR chart observed on the polyisocyanatoisocyanurateprepared in Example 12.

DETAILED EXPLANATION OF THE INVENTION

The aromatic diamines represented by Formula (I) are novel compoundsrecently developed and their properties and a method for preparing thesame are detailed in Japanese Patent Application Serial Nos. (hereunderreferred to as "J.P.A. No(s).") Hei 1-228370 and Hei 1-341120.

A method for preparing the alicyclic diamine represented by Formula (II)according to the present invention will hereinafter be explained in moredetail. The alicyclic diamines of the present invention represented byFormula (II) can be prepared by catalytically reducing the foregoingα-(aminophenyl)alkyl-amine represented by Formula (I): ##STR14## whereinR represents a hydrogen atom or a lower alkyl group having 1 to 5 carbonatoms and the amino group attached to the phenyl group may be in eitherof the 2-, 3- and 4-positions in the presence of a ruthenium catalyst,water or 1,4-dioxane, and an alkali or alkaline earth metal hydroxide.

The aromatic amines represented by Formula (I) may be industriallyeffectively prepared by nitrating alkyl phenyl ketone, which is a cheapindustrial agent and used as a starting material, to give a nitrophenylalkyl ketone and then catalytically reducing it in the presence ofammonia; or nitrating an α-aminoalkylbenzene obtained byreductive-amination of an alkyl phenyl ketone and then catalyticallyreducing the resultant product.

The nitrophenyl alkyl ketone is a nitro compound represented by thefollowing general formula (d): ##STR15## wherein R represents a loweralkyl group having 1 to 5 carbon atoms and the nitro group attached tothe phenyl group may be in either of the 2-, 3- and 4-positions andspecific examples thereof include nitroacetophenone, nitropropiophenone,nitrophenyl propyl ketone. nitrophenyl butyl ketone and nitrophenylpentyl ketone.

Specific examples of the a -(aminophenyl)alkylamine compoundsrepresented by the foregoing Formula (I) include α-(2-aminophenyl)ethylamine, α-(3-aminophenyl)ethlamine, α-(4-aminophenyl) ethylamine,α-(2-aminophenyl)propyl-amine, α-(3-aminophenyl) propylamine,α-(4-aminophenyl)-propylamine, α-(2-aminophenyl) butylamine,α-(3-amino-phenyl)butylamine, α-(4-aminophenyl) butylamine,α-(2-aminophenyl)pentylamine, α-(3-aminophenyl) pentylamine,α-(4-aminophenyl)pentylamine, α-(2-aminophenyl) hexylamine,α-(3-aminophenyl)hexylamine and α-(4-aminophenyl) hexylamine.

Specific examples of the α-(aminocyclohexyl)alkylamines represented byFormula (II) prepared according to the method of the present inventionare α-(2-aminocyclohexyl)ethylamine, α-(3-aminocyclohexyl)ethylamine,α-(4-aminocyclohexyl)ethylamine, α-(2-aminocyclohexyl)propylamine,α-(3-aminocyclohexyl)propylamine, α-(4-aminocyclohexyl)propylamine,α-(2-aminocyclohexyl)butylamine, α-(3-aminocyclohexyl)butylamine,α-(4-aminocyclohexyl)butylamine, α-(2-aminocyclohexyl)pentylamine,α-(3-aminocyclohexyl)pentylamine, α-(4-aminocyclohexyl)pentylamine,α-(2-aminocyclohexyl)hexylamine, and α-(3-aminocyclohexyl)hexylamine,and α-(4-aminocyclohexyl) hexylamine as well as mixture thereof.

Heretofore, the following methods have been known in order to prepare α-(aminocyclohexyl)alkylamines:

(1) a method which comprises reacting 4-vinyl-1-cyclohexane with ammoniain the presence of a zeolite catalyst to giveα-(4-aminocyclohexyl)ethylamine as disclosed in DE No. 3,326,579 (EP No.132,736) and DE No. 3,327,000 (EP No. 133,938); and

(2) a method in which α-(2-aminocyclohexyl)ethylamine is preparedthrough a pyrazoline obtained from 1-acetyl-cyclohexene and hydrazine asdisclosed in DE No. 2,754,553 (U.S. Pat. No. 4,193,905).

However, in the method (1), the reaction is carried out under hightemperature (330° C.) and pressure (275 kg/cm²) conditions and thereaction achieves only a low yield in the order of 5.8%. The method (2)likewise does not achieve satisfactory yield (in the order of 54%).Moreover, the method which comprises reacting 1-acetyl-cyclohexene withhydrazine to cyclize them to thus form3-methyl-4,5-tetramethylene-2-pyrazoline and then catalyticallyhydrogenating the product could not provide α-(3-aminocyclohexyl)ethylamine and α-(4-aminocyclohexyl)ethylamine, but provided only1-methyl-2,3-tetramethylene-1,3-propanediamine, i.e., α-(2-aminocyclohexyl)ethylamine.

The inventors of this invention have conducted various studies to solvethe foregoing problems associated with the method for preparingα-(aminocyclohexyl)alkylamines represented by Formula (II). In otherwords, the inventors have paid attention to α(aminocyclohexyl)ethylaminewhich is the novel diamine disclosed in J.P.A. No. Hei 1-100121, havedeeply investigated the method for the preparation thereof, and havefound that novel α-(aminocyclohexyl alkylamines can be prepared by amethod comprising catalytically reducing α-(aminophenyl)alkylamines(hereinafter referred to as "APRA") in the presence of a catalyst suchas ruthenium.

This compound is in the liquid state at ordinary temperature. Inaddition, it hardly causes side reactions such as decomposition anddeamination during the catalytic reduction. Therefore, it can providethe objective α-(aminocyclohexyl)-alkylamines and mixture thereof in ahigh yield.

As, in the α-(aminocyclohexyl)alkylamines, one of two amino groups isdirectly bonded to the cyclohexyl ring and the other is bonded to thesecondary carbon atom in the hindered form due to the presence of alkylgroups, the reactivity of these amino groups differs from one another.Thus, these compounds have characteristic properties different fromthose for alicyclic diamines such as 2,4-diaminocyclohexyl methane,1,3-bis(amino-methyl)cyclohexane and 4,4'-diamino-dicyclohexyl methanewhich have widely been used conventionally.

More specifically, in the conventionally used diamines, all of the twoamino groups are directly bonded to the cyclohexane ring or a primarycarbon atom and, therefore, the reactivity of these amino groups arealmost the same, while the diamines used in the present invention have asubstantial difference in the reactivity of the amino groups as alreadydiscussed above. In other words, there is an appropriate difference inthe reactivity between these two amino groups and thus it is expectedthat they show characteristic properties as hardening agents for epoxyresins, polyurethanes or polyureas and as starting materials forpolyamides.

Moreover, the α-(aminocyclohexyl)alkylamines represented by Formula (I)have asymmetric carbon atoms and, therefore, they are also effective asagents for optical resolution.

Further, as the α-(aminocyclohexyl)alkylamines have a solidifying pointof not higher than 0° C. and its vapor pressure is relatively low (inthe order of not higher than 0.05 mmHg at 20° C.), they can easily behandled.

The starting materials represented by Formula (I) can be preparedaccording to the following method. First, the nitro group of the nitrocompound represented by Formula (d) is converted into an amino group tothus obtain a compound represented by the following general formula (e):##STR16## and then the carbonyl group of the compound (e) is furtherconverted into an amino group to obtain the diamine compounds of Formula(I). Alternatively, the nitro compound of Formula (d) may directly beconverted into the diamine compounds of Formula (I) through only onestage.

Further, it is also possible to prepare the α-(aminocyclohexyl)alkylamines represented by Formula (I) by reductively aminating alkylphenyl ketones represented by the following general formula (f) to formα-aminoalkylbenzene represented by the following general formula (g),then nitrating the compound (g) to obtain α-(nitrophenyl)alkylaminesrepresented by the following general formula (h) and finally reducingthe nitro group of the compound of Formula (h) to an amino group throughhydrogenation: ##STR17## (in formulae (e) to (h) and (I), R is the sameas that defined above in connection with Formula (II)).

Now, the one-step method will be described in detail below. A startingmaterial of Formula (d) is dissolved in a solvent such as methanol in anSUS autoclave equipped with a stirring machine, a catalyst such as Raneynickel is added to the solution and the solution is stirred.

Then ammonia is introduced into the solution with cooling at 0° to 10°C. and subsequently hydrogen gas is supplied, under pressure, to about40 atm. The temperature is raised to about 70° C. and the reaction isperformed for about 60 minutes. The reaction is finished when thehydrogen gas absorption is completed.

The reaction solution is distilled in vacuo to give a colorless cleardistillate. The distillate is the diamine compound represented byFormula (I).

The catalytic reduction of α-(aminophenyl)alkylamines represented byFormula (I) is performed as follows. First, the foregoing diamine ischarged into an SUB autoclave equipped with a stirring machine, then aruthenium catalyst, water and an alkali or alkaline earth metalhydroxide are added to the diamine and the mixture is heated.Subsequently, hydrogen gas is supplied under pressure up to about 40atm. and the temperature is raised up to a desired level to perform thecatalytic reductive reaction. The reaction is finished when the hydrogengas absorption is completed. After removal of the catalyst, the reactionsolution is distilled in vacuo to obtain a colorless clear distillate.This distillate is the alicyclic diamine compound represented by Formula(II), i.e., α-(aminocyclo-hexyl)alkylamine.

The starting material, α-(aminophenyl)alkylamine, used in the presentinvention has three isomers whose amino group attached to the phenylgroup is present at the 2-, 3- or 4-position. These isomers may be usedalone or in combination as the starting materials of the presentinvention.

The amount of water in the method of this invention preferably rangesfrom 1 to 40% by weight and more preferably 3 to 20% by weight on thebasis of the weight of the α-(amino-phenyl)alkylamine used. This isbecause, if the amount of water is too great, the amount of by-productshaving a low boiling point such as α-aminoalkylbenzene andaminoalkylcyclohexane formed tends to increase and sufficient effect ofinhibiting side reactions by the addition of an alkaline substancecannot sometimes be achieved. On the other hand, if the amount of waterused is too small, the reaction rate is lowered and hence the yield isalso reduced.

Water may be used singly, but may also be used in combination with otherorganic solvents. Such organic solvents which may be used are preferablyhydrophilic ones. Specific examples thereof are alcohols such asethanol, isopropyl alcohol and cyclohexanol.

Examples of the ruthenium catalysts used in the invention include metalruthenium, ruthenium oxide and ruthenium hydroxide. These catalysts arepreferably use in the form supported by a carrier such as carbon,alumina and diatomaceous earth. The amount of these catalysts varydepending on various factors such as the kinds and shapes thereof. Forinstance, if 5% ruthenium/carbon is employed, it is used in an amountranging from 0.1 to 10.0% by weight and preferably 0.5 to 2.5% by weighton the basis of the weight of the starting material:α-(aminophenyl)alkylamine.

Specific examples of the alkali or alkaline earth metal hydroxides usedin the invention are hydroxides of alkali metals such as lithium,potassium and sodium and alkaline earth metals such as barium,strontium, calcium and magnesium. Alternatively, it is also possible toemploy substances which are converted into hydroxides when they come incontact with water such as sodium carbonate and potassium carbonate.However, preferably used are sodium hydroxide and potassium hydroxidefrom the viewpoint of their price and yield of the objective products.

The amount of these alkali or alkaline earth metal hydroxides preferablyranges from about 0.5 to 16 mole % and more preferably 3 to 10 mole %.If the amount of these alkaline substances is small, it is oftenobserved that the formation of by-products cannot sufficiently besuppressed, while if the alkali substance is used in an amount of morethan the upper limit, further improvement in the side-reactioninhibiting effect cannot be achieved.

Hydrogen gas is used in the reaction at a pressure suitably ranging from20 to 120 kg/cm², preferably 30 to 80 kg/cm². The reaction temperaturein general ranges from 50° to 220° C., preferably 80° to 150° C. Theisoration of the objective product from the reaction mixture can beperformed by filtering the mixture, distilling off the water and thereaction solvent and then distilling at a high vacuum.

The method of the present invention makes it possible to reduceα-(aminophenyl)alkylamines to a α-(aminocyclohexyl)-alkylamines in ahigh yield even under relatively mild conditions at a high reaction ratewithout a substantial increase in the amount of by-products. Therefore,the present invention is industrially quite advantageous.

The alicyclic diisocyanates represented by Formula (III) are novelcompounds which have just been developed recently. A method for thepreparation thereof will be explained below.

The alicyclic diisocyanates can be prepared by a method which comprisesdirectly reacting the alicyclic diamines represented by Formula (II)with phosgene or a method which comprises previously preparing a salt ofthe alicyclic diamine such as hydrochloride and then suspending the saltin an inert solvent to react it with phosgene.

The former process is called "cold-hot two-stage phosgenation". Theembodiment of the reaction suffers from no particular restriction. Ingeneral, however, gaseous phosgene is introduced into an inert solventcontained in a reactor while cooling the reaction system at atemperature ranging from 0° to 5° C. to dissolve phosgene in the inertsolvent almost to its saturated solubility in the solvent, the reactorbeing equipped with a phosgene gas inlet and a means for sufficientlystirring the reaction system. Then, a solution of the foregoingalicyclic diamine in the same inert solvent is added to the reactionsystem while introducing gaseous phosgene in an amount 1 to 2 times asmuch as its stoichiometric quantity. In the mean time, the temperatureof the reaction solution is maintained at not higher than 15° C. and thehydrogen chloride generated and excess phosgene are purged out of thereaction system through a reflux condenser. At this stage, the contentsof the reactor form a slurry. The main reaction is the formation ofcarbamyl chloride and amine hydrochlorides. After the addition of theamine solution, the reaction is continued for additional 30 minutes to 2hours. The procedure described above is referred to as "coldphosgenation".

Then the reaction system is heated to a temperature of 80° C. to 160° C.over 30 minutes to 3 hours. Upon raising the temperature, the phosgenedissolved in the solvent is liable to vaporize and foam and thus it ispreferable to reduce the flow rate of phosgene to the order of itsstoichiometric quantity, as opposed to the case of the coldphosgenation. After the temperature has been raised, the reaction iscontinued for additional one to 3 hours. (The procedure described aboveis called the second-stage reaction in the cold-hot two-stage process).When the slurry is completely dissolved, the reaction is assumed to becompleted. The foregoing procedure is called "hot phosgenation". Theprincipal reactions of the hot phosgenation are the decomposition of thecarbamyl chloride to isocyanate and the phosgenation of the aminehydrochlorides into isocyanates.

After completion of the hot phosgenation, the reaction system is heatedto a temperature of 90° to 170° C. and gaseous nitrogen is blown intothe reaction system at a flow rate of not lower than 200 ml/min toremove the dissolved gaseous components and to sufficiently decomposeunreacted carbamyl chloride. Then, following cooling, the inert solventis distilled off under reduced pressure to obtain an alicyclicdiisocyanate.

The latter process is referred to as "phosgenation of aminehydrochloride". The hydrochloride of the alicyclic diamine is preparedin advance. The synthesis of the hydrochloride is effected with ease bythe well-known method of treating an alicyclic diamine with hydrogenchloride or concentrated hydrochloric acid. The thus-formed alicyclicdiamine hydrochloride, which has been fully dried and pulverized, isdispersed in an inert solvent contained in a reactor equipped with meanssimilar to those used in the "cold-hot two-stage phosgenation" processdescribed above. The reaction system is maintained at a temperatureranging from 80° to 160° C., to which system gaseous phosgene isadmitted for 3 to 10 hours so that the total phosgene introduction mayamount to 2 to 10 times as much as its stoichiometric quantity, to thusobtain an isocyanate. The progress of the reaction may be inferred bythe amount of gaseous hydrogen chloride generated, the dissipation ofthe alicyclic diamine as the starting material which is insoluble in thereaction solvent and hence the transparency and homogeneity of thereaction solution. The hydrogen chloride generated and excess phosgeneare discharged through a reflux condenser to the outside of the reactionsystem. After the reaction has been completed, gaseous nitrogen isintroduced into the reaction solvent to remove the dissolved phosgene,and subsequent to cooling and filtration, the inert solvent is distilledout under reduced pressure and further the resulting diisocyanate ispurified by distillation under reduced pressure or the like to obtainthe objective alicyclic diisocyanate of Formula (III).

It is sufficient to introduce phosgene in an amount 2 to 10 times asmuch as its stoichiometric quantity for the both prosesses of "cold-hottwo-stage phosgenation" and "phosgenation of amine hydrochloride".Examples of the inert solvent which may be used include chlorinatedaromatic hydrocarbons such as mono-chlorobenzene and α-dichlorobenzene;and aromatic hydrocarbons such as xylene and toluene; as well as esterssuch as ethyl acetate, butyl acetate and amyl actate.

The synthesis of the alicyclic diisocyanates of Formula (III) proceedsat an industrially acceptable high velocity in a relatively shortreaction time even if the second stage of the cold-hot two stagephosgenation or the phosgenation in the hydrochloride process isperformed at a relatively low temperature. This results in the reductionof the amount of the by-products, in particular carbodiimide compoundsand the formation of the intended products at high selectivity, and thismakes it possible to use a relatively low boiling point withoutperforming the reaction under pressure; to use a variety of inertsolvents; to use various kinds of heating mediums required formaintaining the reaction; and to quite easily remove solvents aftercompletion of the reaction.

α-(3-Isocyanato-cyclohexyl)ethylisocyanate represented by the followingformula (III') (hereinafter referred to as "IECI") which is one of thenovel alicyclic diisocyanates of the present invention shows thefollowing excellent properties compared with conventional diisocyanatecompounds. ##STR18##

First, as seen from Formula (III'), IECI has an isocyanato groupdirectly bonded to the cyclohexane ring as well as an isocyanato groupbonded to the carbon of the alicyclic chain. There is a properdifference in the reactivity with an active hydrogen-containing compoundbetween the both isocyanato groups and for this reason, IECI is expectedto have characteristic properties in such a reaction.

Secondary, the urethane resins, urea resins and polyamide resins derivedfrom IECI of the present invention show appropriate mechanical strengthand heat resistance since IECI has a substituent at the meta-position ofthe cyclohexane ring. Thirdly, IECI of the present invention can beeffectively prepared according to a method which will be explained indetail below and in which α-(aminocyclohexyl)ethylamine (hereinafterreferred to as "ACEA") or a salt thereof is employed as a startingmaterial even on an industrial scale. Moreover, ACEA can be industriallyeffectively prepared from acetone which is an industrial reagent of lowprice.

Fourth, IECI of the present invention is in the liquid state at ordinarytemperature and has a low vapor pressure (in the order of 0.002 mmHg at20° C.). Therefore, it can be relatively easily handled. For instance,the content of isocyanate of α-(isocyanatocyclohexyl)ethylisocyanate is43.3% (theoretical value) which is high compared with those for theconventional alicyclic or aliphatic diisocyanates.

IECI which is one of the alicyclic diisocyanates show the yellowingresistance and ultraviolet light resistance equal to or higher thanthose for the conventional alicyclic or aliphatic diisocyanates.

Further, the polyisocyanato-isocyanurates represented by the generalformula (IV): ##STR19## (wherein R₁ to R₃ may be the same or differentand each represents the following group: ##STR20## (in the formula, Rrepresents a hydrogen atom or a lower alkyl group) and n is an integerof 1 to 5) are also novel compounds which have just been developedrecently. A method for the preparation thereof will now be explainedbelow.

The polyisocyanato-isocyanurates of Formula (IV) can be prepared bypolymerizing isocyanates represented by the above-mentioned generalformula (III) in the presence of an alkali metal compound of acarboxylic acid as a trimerizing catalyst, an alkali metal compound ofcyanic acid and optionally polyethylene oxide compounds or alcohols.

Specific examples of the isocyanate compounds represented by Formula(III) are α-(2-isocyanatocyclohexyl)ethylisocya-nate,α-(2-isocyanatocyclohexyl)methylisocyanate,α-(2-isocyanatocyclohexyl)propylisocyanate,α-(2-isocyanatocyclo-hexyl)butylisocyanate,α-(2-isocyanatocyclohexyl)pentylisocyanate,α-(3-isocyanatocyclohexyl)ethylisocyanate,α-(3-isocyanatocyclohexyl)methylisocyanate,α-(3-isocyanatocyclohexyl)propylisocyanate,α-(3-isocyanatocyclohexyl)butylisocyanate,α-(3-isocyanatocyclohexyl)pentylisocyanate,α-(4-isocyanatocyclohexyl)ethylisocyanate,α-(4-isocyanatocyclohexyl)methylisocyanate,α-(4-isocyanatocyclo-hexyl)propylisocyanate,α-(4-isocyanatocyclohexyl)butylisocyanate,α-(4-isocyanatocyclohexyl)pentylisocyanate.

Examples of the trimerizing catalysts are organic strong bases such asalkali salts of carboxylic acids, alkali metal ferrite, alkali metalcarbonates, tertiary amines, tertiary phosphin, onium compounds of N orP and heterocyclic compounds containing these elements as disclosed inJ. H. Saunders et al., Polyurethanes Chemistry and Technology, 1962, 94.In addition, it is also known to use reaction products of Mannich basesor tertiary amines with phosphoric acid, phosphorous acid or alkylesters of phosphonic acid as disclosed in U.S. Pat. Nos. 4,182,826 and4,499,253. However, if these alkali metal salts of carboxylic acids,which are known catalysts, are employed alone, the intendedtrimerization of the compounds of Formula (III) cannot be achieved.Likewise, such trimerization cannot be achieved if the alkali metalsalts of cyanic acid are used alone.

The inventors of this invention have found that such a trimerizationreaction easily proceeds at a high reaction rate when the alkali metalsalts of carboxylic acid and the alkali metal salts of cyanic acid arecombined and the combined solid catalyst is used as such, compared withthe reaction rates observed when they are separately used in thereaction.

Good results have been obtained when the catalyst is added according tothe following method. First the diisocyanate compound of Formula (III)is admixed with a polyethylene oxide compound for instance, polyethyleneglycol having a molecular weight ranging from 200 to 1,000 andpolyethylene glycol monomethyl ether) or alcohols and then a combinedcatalyst comprising the alkali metal salt of carboxylic acid and thealkali metal salt of cyanic acid is added thereto.

The best result can be achieved when the combined catalyst is added inthe form of a solution in the polyethylene oxide compound or thealcohols. More specifically, it has been found that the trimerizationcan be markedly accelerated and the maintenance of the reaction becomessubstantially easy if the catalyst is used in such a manner.

Specific examples of the metal salts of carboxylic acids used as thetrimerization catalysts are salts of alkali metal and other metals suchas tin, zinc and lead with alkyl carboxylic acids such as acetic acid,propionic acid, butyric acid, valeric acid, caproic acid and octylicacid. Preferred is potassium acetate. Specific examples of the alkalimetal salts of cyanic acid are alkali metal cyanates such as sodiumcyanate, potassium cyanate and lithium cyanate; and cyanates of othermetals such as tin, zinc, lead, silver and gold. Preferred is potassiumcyanate among others.

Specific examples of the polyethylene oxide compounds are polyethyleneglycols having a molecular weight ranging from 200 to 1,000,polyethylene glycol monomethyl ether and polyethylene glycol dimethylether and preferred is polyethylene glycol having a molecular weight of400.

Specific examples of the alcohols which can be used in the presentinvention are methanol, ethanol, butanol, ethylene glycol,1,3-butanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol,trimethylolpropane, polypropylene glycol and phenol.

Regarding the amount of the catalyst, it has been found that thetrimerization can markedly be accelerated if the alkali metal salt ofcyanic acid is used in an amount ranging from 0.05 to 20 moles and thepolyethylene oxide compound or an alcohol is used in an amount rangingfrom 1 to 50 moles per mole of the metal salt of carboxylic acid.

As the reaction solvents, there may be used in the present inventionorganic solvents usually employed in the preparation of isocyanates.Specific examples of solvents preferably used in the invention areesters such as ethyl acetate and butyl acetate; ketones such as acetoneand methyl ethyl ketone; aromatic substances such as benzene, tolueneand xylene; and aprotic solvents such as dimethylsulfoxide,tetramethylsulfone, tetrahydrofuran, N-methylpyrrolidone,N,N-dimethylformamide, N,N'-tetramethyl urea and1,3-dimethylimidazolidinone.

When a solvent is used, or even when it is not used, a solutioncomprising the foregoing potassium acetate, potassium cyanate,polyethylene glycol having a molecular weight of 400, and optionally asolvent, is previously prepared and is added to the reaction system. Thereaction time can be adjusted by appropriately selecting the amount ofthe catalyst and the reaction temperature.

The temperature of the trimerization ranges from 0° to 15° C. preferably30° to 80° C.

Moreover, as a reaction stopping agent, there may be used, for instance,acids such as sulfuric acid, orthophosphoric acid, polyphosphoric acid,p-toluenesulfonic acid, acetic acid, trifluoroacetic acid andbenzenesulfonic acid; and acid chlorides such as benzoyl chloride andacetyl chloride.

The coloring observed during the trimerization reaction can effectivelybe prevented by the addition of an antioxidant as a stabilizer to thereaction system prior to the initiation of the reaction.

As such reaction stabilizers or storage stabilizers, organic phosphoricacid compounds and phenolic compounds can be used. Specific examplesthereof are 2,6-di-tert-butyl-4-methylphenol, triphenyl phosphite,triethyl phosphite and diisodecylpentaerythritol diphosphite.

Specific examples of the compounds of Formula (IV) in which n is 1include N,N',N"-tris(2-(α-isocyanatoethyl)cyclohexyl) isocyanurate,N,N',N"-tris(2-isocyanato-α-ethylcyclohexyl) isocyanurate,N,N',N"-tris(2-isocyanato-cyclohexylmethyl)isocyanurate,N,N',N"-tris(2-(α-isocyanatopropyl)cyclohexyl) isocyanurate,N,N',N"-tris(2-isocyanato-α-cyclohexyl-propyl) isocyanurate,N,N',N"-tris(2-(α-isocyanatobutyl)-cyclohexyl) isocyanurate,N,N',N"-tris(2-isocyanato-α-cyclo-hexylbutyl) isocyanurate,N,N',N"-tris(2-(α-isocyanato-pentyl)cyclohexyl) isocyanurate,N,N',N"-tris(2-isocyanato-α-cyclohexylpentyl) isocyanurate,N,N',N"-tris(3-(α-isocyanato-ethyl)cyclohexyl) isocyanurate,N,N',N"-tris(3-isocyanato-α-ethylcyclohexyl) isocyanurate,N,N',N"-tris(3-isocyanato-cyclohexylmethyl) isocyanurate,N,N',N"-tris(3-(α-isocyanato-propyl)cyclohexyl) isocyanurate,N,N',N"-tris(3-isocyanato-α-cyclohexylpropyl) isocyanurate,N,N',N"-tris(3-(α- isocyanatobutyl)cyclohexyl) isocyanurate,N,N',N"-tris(3-isocyanato-α-cyclohexylbutyl) isocyanurate,N,N',N"-tris(3- (α-isocyanatopentyl)cyclohexyl) isocyanurate,N,N',N"-tris(3-isocyanato-α-cyclohexylpentyl) isocyanurate,N,N',N"-tris(4-(α-isocyanatoethyl)cyclohexyl) isocyanurate,N,N',N"-tris(4-isocyanatoα-cyclohexylethyl) isocyanurate,N,N',N"-tris(4-isocyanatomethyl)-cyclohexyl) isocyanurate,N,N',N"-tris(4-isocyanato-cyclohexylmethyl) isocyanurate,N,N',N"-tris(4-(α-isocyanatopropyl)cyclohexyl) isocyanurate,N,N',N"-tris(4-isocyanato-α-cyclohexylpropyl) isocyanurate,N,N',N"-tris(4-(α-isocyanatobutyl)cyclohexyl) isocyanurate,N,N',N"-tris(4-isocyanato-α-cyclohexylbutyl) isocyanurate,N,N',N"-tris(4-(α-isocyanatopentyl)cyclohexyl) isocyanurate,N,N',N"-tris(4-isocyanato-α-cyclohexylpentyl) isocyanurate,N,N'-bis(2-(α-isocyanatoethyl)-cyclohexyl)-N"-(2-(α-isocyanatopropyl)cyclohexyl)-isocyanurate,N,N'-bis(2-isocyanato-α-cyclohexylethyl)-N"-(2-(isocyanato-α-cyclohexylpropyl)isocyanurate,N,N'-bis(2-isocyanato- methyl)cyclohexyl)-N"-(2-(α-isocyanatoethyl)cyclohexy)isocyanurate,N,N'-bis(2-isocyanato-cyclohexylmethyl)-N"-(2-isocyanato-α-cyclohexylethyl)isocyanurate,N,N'-bis(3-(α-isocyanatoethyl)cyclohexyl)-N"-(3-(α-isocyanatopropyl)cyclohexyl)isocyanurate,N,N'-bis(3-iso-cyanato-α-cyclohexyl-ethyl)-N"-(3-(isocyanato-α-cyclohexylpropyl)isocyanurate,N,N'-bis(3-isocyanatomethyl)cyclohexyl)-N"-(3-(α-isocyanatoethyl)cyclohexy)isocyanurate,N,N'-bis(3-isocyanato-cyclo-hexylmethyl)-N"-(3-isocyanato-.alpha.-cyclohexyl-ethyl)isocyanurate,N,N'-bis(4-(α-isocyanato-ethyl)cyclohexyl)-N"-(4-(α-isocyanato-propyl)cyclohexyl)isocyanurate,N,N'-bis(4-isocyanato-α-cyclohexylethyl)-N"-(4-(isocyanato-α-cyclohexylpropyl)isocyanurate,N,N'-bis(4-isocyanatomethyl)cyclohexyl)-N"-(4-(α-isocyanato-ethyl)cyclohex)iso-cyanurate,N,N'-bis(4-isocyanato-cyclohexylmethyl)-N"-(4-isocyanato-α-cyclohexylethyl)isocyanurate, N,N'-bis(4-α-isocyanatoethyl)cyclohexyl)-N"-(3-(α-isocyanatoethyl)cyclohexyl)isocyanurate,N,N'-bis(4-isocyanato-α-cyclohexylethyl)-isocyanurate-N"-(3-isocyanato-α-cyclohexylethyl)isocyanurate,N,N'-bis(4-isocyanatomethyl)-cyclohexyl)-N"-(3-(isocyanatomethyl)-cyclohexyl)isocyanurate,N,N'-bis(4-isocyanato-cyclohexy-methyl-N"-(3-isocyanato-cyclohexyl-methyl)isocyanurate,N,N'-bis(4-(α-isocyanatopropyl)cyclohexyl)-N"-(3-(α-isocyanato- propyl)cyclohexyl)isocyanurate,N,N'-bis(4-isocyanato-α-cyclohexylpropyl)-N"-(3-isocyanato-α-cyclohexylpropyl)isocyanurate,N,N'bis(4-(α-isocyanatoethyl)cyclohexyl)-N"-(2-(α-isocyanato-ethyl)cyclo-hexyl)isocyanurate, N,N'-bis(4-isocyanato-α-cyclohexylethyl)isocyanurate-N"-(2-isocyanato-α-cyclohexyl-ethyl) isocyanurate,N,N'-bis(4-isocyanatomethyl)-cyclohexyl)-N"-(2- isocyanato-methyl)-cyclohexyl)isocyanurate,N,N'-bis(4-isocyanatocyclohexylmethyl)-N"-(2-isocyanato-cyclohexyl-methyl)isocyanurate,

N,N'-bis(4-(α-isocyanatopropyl)cyclohexyl)-N"-(2-(α-isocyanatopropyl)cyclohexyl)isocyanurate,N,N'-bis(4-isocyanato-α-cyclohexyl-propyl)-N"-(2-isocyanato-α-cyclohexyl-propyl)isocyanurate,N,N'-bis(3-(α-isocyanato-ethyl)cyclohexyl)-N"-(2-(α-isocyanato-ethyl)cyclohexyl)isocyanurate,N,N'-bis(3-isocyanato-α-cyclohexyl-ethyl)-isocyanurate-N"-(2-isocyanato-α-cyclohexyl-ethyl)isocyanurate,N,N'-bis(3-isocyanatomethyl)cyclohexyl)-N"-(2-(isocyanato-methyl)-cyclohexyl)isocyanurate,N,N'-bis(3-isocyanato-cyclohexyl-methyl)-N"-(2-isocyanatocyclohexylmethyl)isocyanurate,N,N'-bis(3-(α-isocyanato-propyl) cyclohexyl)-N"-(2-(α-isocyanato-propyl)cyclohexyl)isocyanurate,N,N'-bis(3-isocyanato-α-cyclohexyl-propyl)-N"-(2-(isocyanato-α-cyclohexyl-propyl)isocyanurate,N,N'-bis(3-(α-isocyanato-ethyl)cyclohexyl)-N"-(4-(α-isocyanato-ethyl)cyclohexyl) isocyanurate,N,N'-bis(3-isocyanato-α-cyclohexylethyl)isocyanurate-N"-(4-isocyanato-α-cyclohexyl-ethyl)isocyanurate,N,N'-bis(3-isocyanatomethyl)cyclohexyl)-N"-(4-(isocyanato-methyl)-cyclohexyl)isocyanurate,N,N'-bis(3-isocyanato-cyclohexyl-methyl)-N"-(4-isocyanato-cyclohexylmethyl)isocyanurate,N,N'-bis(3-(α-isocyanatopropyl)cyclohexyl)-N"-(4-(α-isocyanato-propyl)cyclohexyl) isocyanurate,N,N'-bis(3-isocyanato-α-cyclohexyl-propyl)-N"-(4-(isocyanato-α-cyclohexylpropyl)isocyanurate,N,N'-bis(2-(α-isocyanato-ethyl)cyclohexyl)-N"-(3-(α-isocyanato-ethyl)-cyclohexyl)isocyanurate,N,N'-bis-(2-isocyanato-α-cyclohexylethyl)-N"-(3-isocyanato-α-cyclohexylethyl)isocyanurate,N,N'-bis(2-isocyanatomethyl)-cyclohexyl)-N"-(3-(isocyanatomethyl)cyclohexyl)isocyanurate,N,N'-bis(2-isocyanato-cyclohexylmethyl)-N"-(3-isocyanato-cyclohexylmethyl)isocyanurate,N,N'-bis(2-(α-isocyanato-propyl)cyclohexyl)-N"-(3-(α-isocyanatopropyl)cyclohexyl)isocyanurate,N,N'-bis(2-isocyanato-α-cyclohexyl-propyl)-N"-(3-(isocyanato-α-cyclohexylpropyl)isocyanurate,N,N'-bis(2-(α-isocyanatoethyl)cyclo-hexyl)-N"-(4-(α-isocyanato-ethyl)cyclohexyl)isocyanurate,N,N'-bis-(2-isocyanato-α-cyclohexyl-ethyl)-isocyanurate-N"-(4-isocyanato-α-cyclohexylethyl)isocyanurate,N,N'-bis(2-isocyanatomethyl)cyclohexyl)-N"-(4-(isocyanato-methyl)-cyclohexyl)isocyanurate,N,N'-bis(2-isocyanato-cyclohexyl-methyl)-N"-(4-isocyanato-cyclohexyl-methyl)isocyanurate,N,N'-bis(2-(α-isocyanatopropyl)cyclohexyl)-N"-(4-(α-isocyanatopropyl)cyclohexyl)isocyanurate,N,N'-bis(2-isocyanato-α-cyclohexyl-propyl)-N"-(4-(isocyanato-α-cyclohexyl-propyl)isocyanurate,N-(3-(α-isocyanato-ethyl)cyclohexyl)-N',N"-bis(3-(α-isocyanatopropyl)cyclohexyl)isocyanurate,N-(3-isocyanato-α-cyclohexyl-ethyl)-N',N"-bis(3-isocyanato-α-cyclohexyl-propyl)isocyanurate,N-(3-isocyanato-methyl)cyclohexyl)-N',N"-bis(3-α-isocyanato-ethyl)-cyclohexyl)isocyanurate,N-(3-isocyanato-cyclohexyl-methyl)-N',N"-bis(3-isocyanato-α-cyclohexyl-ethyl)isocyanurate,N-(2-(isocyanatoethyl)cyclohexyl)-N',N"-bis(2-(α-isocyanatopropyl)cyclohexyl)isocyanurate,N-(2-isocyanato-cyclohexylethyl)-N',N"-bis(2-isocyanato-cyclohexyl-propyl)isocyanurate,N-(2-(isocyanatomethyl)cyclohexyl)-N',N"-bis(2-(α-isocyanato-ethyl)cyclohexyl)isocyanurate,N-(2-iso-cyanato-cyclohexylmethyl)-N',N"-bis(2-isocyanato-α-cyclohexylethyl)-isocyanurate,N-(4-isocyanatomethyl)cyclohexyl)-N',N"-bis(4-(αisocyanato-ethyl)cyclohexyl)isocyanurate,N-(4-isocyanato-cyclohexyl-methyl)-N',N"-bis(4-isocyanato-α-cyclohexylethyl)isocyanurate,N-(4-α-isocyanato-ethyl-cyclohexyl)-N',N"-bis(4-(α-isocyanatopropyl)cyclohexyl)isocyanurate andN-(4-isocyanato-α-cyclohexyl-ethyl)-N',N"-bis(4-(isocyanato-α-cyclohexylpropyl)isocyanurate.

Moreover, examples of the compounds of Formula (IV) in which n is 2, 3,4 or 5, are oligonmers corresponding to those listed above.

Preferred embodiments of the method for preparing the objectivecompounds of Formula (IV) will now be explained below.

First, a solvent for dissolving the objective compound (IV) is selectedand prepared. Examples of such solvents are butyl acetate, ethylacetate, cellosolve acetate, acetone, methy ethyl ketone, benzene,toluene and xylol.

The amount of the solvent selected ranges from 5 to 150 parts by weightper 100 parts by weight of the compound of Formula (III). this respect,the compound of Formula (III) may be used alone or in combination in aproper ratio. The preparation thus obtained is referred to as principalstarting material A. It is herein noted that if the compound is used inan amount of less than 5% by weight, the objective product can beobtained, but its yield achieved is not industrially acceptable.

Separately, a mixture containing a catalyst or the like (hereinafterreferred to as "catalyst B") and a mixture containing a reactionstopping agent (hereinafter referred to as "reaction stopping agent C")are prepared.

More specifically, the catalyst B is obtained by dissolving, in thesolvent used for preparing the principal material A, an alkali metalsalt of carboxylic acid, an alkali metal salt of cyanic and apolyethylene oxide compound or an alcohol as the trimerization catalystand a stabilizer. Regarding the mixing ratio, the alkali metal salt ofcarboxylic acid is used in an amount ranging from 1 to 10% by weight onthe basis of the weight of the solvent; the amount of the alkali metalsalt of cyanic acid ranges from 0.05 to 20.0 moles and preferably 0.2 to0.8 mole; that of the polyethylene oxide compound or the alcohol rangesfrom 1.0 to 50 moles and that of the stabilizer ranges from 0.01 to 0.5mole, preferably 0.05 to 0.1 mole, per mole of rhe alkali metal salt ofcarboxylic acid. The amount of the alkali metal salt of carboxylic acidranges from 0.0001 to 0.1 mole, preferably 0.001 to 0.01 mole per moleof the solute (diisocyanate) of the principal material A.

The stabilizer also serves to inhibit the coloring and the change ofproperties of the objective products during reaction and storing.

The reaction stopping agent C can be prepared by dissolving the reactionstopping agent in the solvent used for preparing the principal materialA. The amount thereof dissolved in the solvent ranges from 0.5 to 5% byweight on the basis of the weight of the solvent. The reaction stoppingagent is used in an amount ranging from 0.001 to 0.5% by weight,preferably 0.01 to 0.3% by weight on the basis of the total weight ofthe solute (diisocyanate) of the principal material A.

A reaction vessel which is equipped with a stirring machine, athermometer, a dropping funnel, a reflux condenser and a pipe forintroducing an inert gas is used in the reaction by taking intoconsideration that this reaction system undergoes a liquid-liquid mixingreaction. The reaction vessel is preferably provided with a means forcontrolling the temperature of the reaction system such as those capableof heating, heat retaining or cooling the system.

A desired amount of the principal material A is introduced into thereaction vessel or a diisocyanate of Formula (II) and a solvent areintroduced into the vessel and the diisocyanate is dissolved in thesolvent at a room temperature to prepare the principal material A andthe reaction system is stirred while being blanketed with an inert gassuch as nitrogen or argon gas, wherein the temperature is maintained at20° to 3020 C.

The catalyst B is dropwise added to the solution, the temperature israised to T° C. and the reaction is continued for 1.0 to 15 hours. Inthis case, the temperature T ranges from 0° to 150° C. preferably 30° to80° C. If the temperature is lower than 0° C., the objectivepolyisocyanato-isocyanurate can be obtained, but the yield and/or thereaction rate are not industrially acceptable, while if it is higherthan 150 ° C, the polyisocyanato-esocyanurate can of course be obtained.However, the yield of the product of Formula (I) wherein n is 1decreases, while not only that for each product of Formula (I) in whichn is 2, 3, 4 or 5 is increased, but also the product having n of 6 orhigher is increased.

The progress of the reaction can be monitored by determining the amountof NCO present in the reaction system; or by measuring the quantity ofunreacted monomers in terms of gas chromatography. In general, if theconversion reaction excessively proceeds, the viscosity of the productincreases and the compatibility with the polyol is lowered. Therefore,generally the degree of conversion is controlled to a low level to thusremain unreacted raw materials in the reaction system and the unreactedmaterials are removed after stopping the reaction.

When the reaction proceeds to a desired degree of conversion, adeactivator for the catalyst such as phosphoric acid is added and thenthe temperature of the reaction system is returned to room temperaturewith stirring. The unreacted monomers and the solvent are removed by,for instance, a continuous distillation technique or solvent-extractiontechnique.

The analysis and identification of the resulting products are performedas follows:

The methylcarbamate compound which has been obtained by reacting thereaction product with methyl alcohol is subjected to gel permeationchromatography (GPC) measurement. The molecular weight distribution ofthe compound is determined by the compositional analysis thereof interms of HSLC by the GPC column.

The inventors of this invention have conducted various studies to solvethe problems associated with the conventional two-pack urethane coatingmaterials, have found that the resins for two-pack urethane coatingmaterials which comprise the polyisocyanatoisocyanurate represented byFormula (IV) and a polyol compound are excellent in drying propertiesand weatherability and thus have completed the present invention.

Consequently, the present invention relates to a resin composition fortwo-pack urethane coating materials which comprises an organicpolyisocyanate containing 10 to 100% by weight of thepolyisocyanato-isocyanurate of Formula (IV) and a compound having atleast two active hydrogen atoms in the molecule.

In the foregoing resin composition, the equivalent ratio of the organicpolyisocyanate to the compound having active hydrogen atoms ranges from0.1:1 to 10:1, preferably 0.5 to 2.0 and more preferably 0.8 to 1.2.

The organic polyisocyanate containing 10 to 100% by weight of thepolyisocyanato-isocyanurate of Formula (IV) which is used in the resincomposition for two-pack urethane coating materials according to thepresent invention herein means a polyisocyanate obtained through theforegoing trimerization reaction, or a mixture thereof with a modifiedproduct of an aliphatic or alicyclic compound such as hexamethylenediisocyanate, isophorone diisocyanate or 4,4'-dicyclohexylmethanediisocyanate obtained through the reaction with urethane and/or biuret.

In this mixture, if the amount of the polyisocyanato esocyanuraterepresented by Formula (IV) is less than 10% by weight, it is difficultto obtain resins for two-pack urethane coating materials having gooddrying properties.

Examples of the compounds having at least two active hydrogen atoms usedin the invention are glycols, alkane polyols, polyether polyols,polyester polyol resins, acryl polyol resins, epoxy resins or monomersor polymers of aromatic or heterocyclic polyhydric alcohols.

Specific examples thereof include glycols such as ethylene glycol,propylene glycol, beta,beta'-dihydroxydiethyl ether (diethylene glycol),dipropylene glycol, 1,4-butylene glycol, 1,3-butylene glycol,1,6-hexamethylene glycol, neopentyl glycol, polyethylene glycol,polypropylene glycol, polypropylene-poly-ethylene glycol andpolybutylene glycol; alkane polyols such as glycerin,trimethylolpropane, hexanetriol, pentaerythritol, xylitol and sorbitol;polyether polyols obtained by adding an alkylene oxide or mixturethereof (for instance, ethylene oxide, propylene oxide and 1,2-butyleneoxide) to a polyhydric alcohol or mixture thereof such as glycerin orpropylene glycol; polyether polyols such as those obtained by reactingalkylene oxide with polyfunctional compounds such as ethylenediamine orethanolamine; polyester polyol resins such as those obtained bycondensing a polyhydric alcohol or mixture thereof selected from thegroup consisting of, for instance, ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, 1,4-butylene glycol, 1,3-butyleneglycol, 1,6-hexamethylene glycol, neopentyl glycol, glycerin andtrimethylolpropane with a dibasic acid or mixture thereof selected fromthe group consisting of succinic acid, adipic acid, sebacic acid, dimeracids, maleic anhydride, phthalic anhydride, isophthalic acid andterephthalic acid; acryl polyols obtained by, for instance,copolymerizing polymerizable monomer having at least one active hydrogenin the molecule with copolymerizable other monomers; acryl polyol resinssuch as those obtained by polymerizing acryl esters having activehydrogen atoms (for instance, 2-hydroxyethyl acrylate, 2-hydroxypropylacrylate and 2-hydroxybutyl acrylate), methacrylates having activehydrogen atoms (for instance, 2-hydroxyethyl methancrylate,2-hydroxypropyl methacrylate and 2-hydroxybutyl methacrylate), acrylicacid monoester or methacrylic acid monoester of glycerin, acrylic acidmonoester or methacrylic acid monoester of trimethylolpropane or mixturethereof; with acrylic acid esters (for instance, methyl acrylate, ethylacrylate, isopropyl acrylate, n-butyl acrylate and 2-ethylhexylacrylate), methacrylic acid esters (for instance, methyl methacrylate,ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate,isobutyl methacrylate, n-hexyl methacrylate and lauryl meth-acrylate) ormixture thereof; in the presence of or absence of unsaturated carboxylicacids (for instance, acrylic acid, methacrylic acid, maleic acid anditaconic acid), unsaturated amides (for instance, acrylamide, N-methylolacrylamide and diacetone acrylamide), or other polymerizable monomers(for instance, glycidyl methacrylic acid, styrene, vinyl toluene, vinylacetate and acrylonitrile) or mixture thereof; and epoxy resins such asthose novolak type, β-methylepichlo type, cyclic oxirane type, glycidylether type, glycidyl ester type, glycol ether type, epoxylated aliphaticunsaturated compound type, epoxylated aliphatic ester type,polycarboxylic acid ester type, aminoglycidyl type, halogenated type andresorcin type ones. Monosaccharides such as fruit sugar, grape sugar,cane sugar, milk sugar, 2-methyl glycoside and derivatives thereof; andaromatic or heterocyclic polyhydric alcohols such as trimethylolbenzeneand tris(2-hydroxyethyl)isocyanurate are also included in addition tothe foregoing compounds. These compounds may be used alone or incombination or further in combination with at least one member selectedfrom the group consisting of other compounds having at least two activehydrogen aroms such as primary or secondary amino group-containingcompounds (for instance, ethylenediamine, triethylenediamine,hexamethylene-diamine, m-xylylenediamine, diaminodiphenylmethane,isophorone-diamine, diethylenetriamine, polyamines such as thoseobtained by adding various alkylene polyamines to alkylene oxides andN,N'-dimethyl-ethylenediamine), substituted urea compounds (forinstance, N,N'-dimethyl urea and N-methyl-N'-cyclohexyl urea), mercaptogroup-containing compounds (for instance, 1,2-ethane-dithiol,1,6-hexanedithiol, polyether polythiol and polyester polythiol),carboxyl group-containing compounds (for instance, succinic acid, adipicacid, sebacic acid, terephthalic acid and polybutadiene having carboxyltermini), or compounds having different groups containing activehydrogen atoms in the molecule (for instance, monoethanolamine,thioethanolamine, lactic acid and β-alanine).

Although various compounds having active hydrogen atoms have beenexemplified above specifically, the present invention is not restrictedto the compounds specifically listed above and any compounds havingactive hydrogen atoms may be employed so far as they can react withpolyisocyanates used in making resin compositions for two-pack urethanecoating materials according to the present invention and any combinationof these compounds may be employed.

When the both components of the resin compositions for two-pack urethanecoating materials according to the present invention are mixed together,appropriate solvents may optionally be used. e.g. a solvent is properlyselected, depending on the purposes and applications, from the groupconsisting of, for instance, hydrocarbons (for instance, benzene,toluene, xylene, cyclohexane, mineral spirits and naphtha), ketones (forinstance, acetone, methyl ethyl ketone methyl isobutyl ketone) andesters (for instance, ethyl acetate, n-butyl acetate, cellosolve acetateand isobutyl acetate). These solvents may be used alone or incombination.

The resin compositions of the present invention may further compriseother additives commonly employed in this field, depending on thepurposes and applications, such as catalysts, pigments, leveling agents,antioxidants, plasticizers and surfactants.

Specific examples of such catalysts used in the invention aretriethylamine, triethylenediamine, stannous octoate, dibutyl tindi-2-ethylhexoate, lead 2-ethylenehexoate (Pb 24%), sodium0-phenylphenate, potassium oleate, bismuth nitrate,tetra-(2-ethyl-hexyl) titanate, stannic chloride, ferric chloride,ferric 2-ethylhexoate (Fe 6%), cobalt 2-ethylhexoate (Co 10%), zincnaphthenate (Zn 14.5%), antimony trichloride, N-methylmorpholine,N,N-dimethylbenzylamine, N-ethylmorpholine, N,N-dimethyllauryl-amine,N,N-dimethylpiperazine, N,N,N',N'-tetramethylethylenedi-amine,N,N,N',N'-tetr amethylpropyldiamine,N,N,N',N'-tetramethyl-1,3-butanediamine, hexamethylenetetramine, cobaltnaphthenate, tetra-n-butyl tin, tri-n-butyl tin acetate and dibutyl tindilaurate.

Specific examples of the pigments usable in the invention includepotassium titanate fibers (available from Ohtsuka Kagaku), aluminumoxide (for instance, Emery available from SUMITOMO METAL MINING CO.,LTD.), silica, titanium oxide, Fillite (available from Nippon FilliteCo., Ltd.), metal providers (such as copper and copper alloy powders,iron and iron alloy powders, nickel and nickel alloy powders, and zinc,tin, lead, aluminum and magnesium powders), mica and Suzorite mica(available from U.S. Marietta Resources International Inc.). Inaddition, as anticorrosive paints there may be mentioned, for instance,zinc chromate (available from Nihon Muki Kagaku Kogyo kk), Moly-white(available from Nihon Shawin-Williams Chemical k.k.) and titaniumdioxide (available from TEIKOKU KAKO CO., LTD.).

Specific examples of the leveling agents usable in the present inventionare organic modified polysiloxanes (available from Parker Corporationunder the trade name Of EFKA™-30, 31, 34, 35) and specific examples ofthe antioxidants are Addital XL 109 and 297 (available from Hoechst Co.,Ltd.).

The resin composition for two-pack urethane coating materials accordingto the present invention is used by mixing, immediately before forming apolyurethane resin, the aforesaid organic polyisocyanate and activehydrogen-containing compound as well as solvents and/or other additivesselected depending on the purposes and applications and the compositionmay be used at a temperature ranging from room temperature to 150° C.

The composition of the present invention as a two-pack coating materialshows excellent adhesion to materials to be coated therewith such asmetals, plastics, rubbers, leathers and concrete and thus can widely beemployed in a variety of fields such as vehicles, equipments andinstallations, construction materials and woodworking products.

In general, polyurethane coating materials have adhesion to materials tobe coated therewith, hardness and flexibility which are well-balancedwith each other and are excellent in resistance to cracking, waterresistance, resistance to chemicals, luster and appearance. On the otherhand, the polyurethane coating obtained by applying the composition ofthe present invention as a coating material shows excellentweatherability and photostability in addition to the foregoingproperties. Further, the coated film provides the following excellentcharacteristics compared with commercially available coating materials.First, the isocyanurate type polyisocyanate used in the composition ofthe invention has high initial curing and drying properties comparedwith aliphatic polyisocyanates such as organic polyisocyanates derivedfrom hexamethylene diisocyanate and is excellent in compatibility.Therefore, the coated film has very excellent appearance and coated filmperformance thereof are comparable to or higher than those for coatedfilms derived from commercially available coating materials. Thus, theyare favorable for use in applications such as coating of vehicles inwhich workability, appearance and coated film performance are regardedas of major importance.

The present invention will hereinafter be explained in more detail withreference to the following Examples, but the invention is not restrictedto these specific Examples.

EXAMPLE 1 Preparation of α-(3-aminocyclohexyl)ethylamine

To a 400 ml inner volume SUS 316L autoclave equipped with a stirringmachine, there were added 50.2 g (0.369 mole) ofα-(3-aminophenyl)ethylamine (APEA), 12.1 g of water, 1.20 g (solidcontent) of 5% ruthenium/carbon catalyst and 1.2 g (0.03 mole) offlake-like sodium hydroxide, the internal atmosphere was replaced withnitrogen gas and the content of the autoclave was stirred for a while.Then, hydrogen gas was introduced into the autoclave under pressure to apressure of 40 kg/cm² G and thereafter the temperature was raised up to110° C. Hydrogen gas was further introduced thereinto under pressure toa pressure of 80 kg/cm² G, but it was absorbed as the reaction proceededand correspondingly its pressure was reduced. Thus, the reaction wascontinued while hydrogen gas was intermittently introduced so that thepressure thereof was maintained at a level ranging from 60 to 80 kg/cm²G. During the reaction, the temperature was adjusted to 110° C. Theabsorption of hydrogen gas did not take place any more at the time whenthe total amount of hydrogen gas absorbed reached about 24.8 Nl(corresponding to the stoichiometric amount) and, therefore, thereaction was stopped. The reaction mixture was cooled to roomtemperature, it was removed and filtered. After removing water from thefiltrate by distillation in vacuo, distillation was further carried outat a pressure of 3 to 6 mmHg to obtain 4.5 g (yield 81.1%) of adistillate having a distillation range of 83° to 93° C.

The resulting liquid was colorless and clear and was identified to beα-(3-aminocyclohexyl)ethylamine in terms of elemental analysis, GC-MCspectra, IR spectra, ¹ H-NMR spectra. The results thus observed arelisted below or shown in the attached Figs. In addition, the puritythereof as determined by gas chromatography was found to be 99.7%.

(1) Elemental Analysis (for C₈ H₁₈ N₂):

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             67.55        12.76  19.69                                        Found (%)    67.30        13.00  19.49                                        ______________________________________                                    

(2) GC-MC Spectra: EI-MS Spectra: (M⁺)=142; (Note: Molecular weight ofACEA (C₈ H₁₈ N₂)=142.2)

(3) IR Spectra (rock salt plate; neat): IR spectrum chart is shown inFIG. 1. cm⁻¹ : 3300˜3400; 2880˜3050; 1610; 1460; 1380

(4) ¹ H-NMR spectra (100 MHz, solvent: CDCl₃):

The NMR spectrum chart of the product is shown in FIG. 2.

COMPARATIVE EXAMPLE 1

The same procedures used in Example 1 were repeated except that waterand the flake-like sodium hydroxide were not used, that the stirring wasinitiated when the temperature was raised to 110° C. and that thereaction mixture was stirred for about 12 hours at a hydrogen gaspressure of 80 to 70 kg/cm². The reaction solution was analyzed by gaschromatography and the yield of α-(3-aminocyclohexyl) ethylamine wasfound to be 20 mole % or less.

COMPARATIVE EXAMPLE 2

The same procedures used in Example 1 were repeated except that waterwas not used, that the stirring was initiated when the temperature wasraised to 110° C. and that the reaction mixture was stirred for about 10hours at a hydrogen gas pressure of 80 to 60 kg/cm². The reactionsolution was analyzed by gas chromatography and the yield ofα-(3-aminocyclohexyl)ethylamine was found to be 33 mole %.

EXAMPLE 2 Preparation of α-(3-aminocyclohexyl)ethylamine

To a 400 ml inner volume BUS 316L autoclave equipped with a stirringmachine, there were added 50.2 g (0.369 mole) ofα-(3-aminophenyl)ethylamine (APEA), 50 g of 1,4-dioxane, 1.5 g (solidcontent) of 5% ruthenium/alumina catalyst and 2.5 g of sodium carbonate,the internal atmosphere was replaced with nitrogen gas. Then, hydrogengas was introduced into the autoclave under pressure to a pressure of 40kg/cm² G and thereafter the temperature was raised up to 110° C. andthen the stirring of the reaction mixture was initiated. Hydrogen gaswas absorbed as the reaction proceeded during the temperature was raisedto 200° C. and correspondingly hydrogen gas pressure was reduced. Thus,the reaction was continued while hydrogen gas was intermittentlyintroduced so that the pressure thereof was maintained at a levelranging from 50 to 30 kg/cm² G. During the reaction, the temperature wasadjusted to 200° C. The absorption of hydrogen gas did not take placeany more at the time when the total amount of hydrogen gas absorbedreached about 21.1 Nl and, therefore the reaction was stopped. Thereaction mixture was cooled to room temperature, removed from theautoclave and filtered. After removing water from the filtrate bydistillation in vacuo, distillation was further carried out at apressure of 2 to 4 mmHg to obtain 32.2 g (yield 61.4%) of a distillatehaving a distillation range of 73° to 84° C.

As in Example 1, the resulting liquid was identified to beα-(3-aminocyclohexyl)ethylamine in terms of ¹ H-NMR spectra, GC-MCspectra and IR spectra. The result of elemental analysis are as follows:

Elemental Analysis (for C₈ H₁₈ N₂):

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             67.55        12.76  19.69                                        Found (%)    67.31        13.10  19.47                                        ______________________________________                                    

In addition, the purity of the product as determined by gaschromatography was found to be 99.7%.

The starting material, APEA, for preparing ACEA of the present inventionwas prepared according to the following reference Example 1.

REFERENCE EXAMPLE 1 Preparation of a α-(3-aminophenyl)ethylamine

To a 500 ml inner volume SUS 316L autoclave equipped with a stirringmachine, there were added 33.0 g (0.2 mole) of a m-nitroacetophenone,200 ml of methanol and 4.6 g (expressed in the amount of nickel) ofRaney nickel, the internal atmosphere was replaced with nitrogen gas andthe contents of the autoclave were stirred for a while.

While cooling the autoclave with ice-water, about 40 g of ammonia wasadded thereto. Then, hydrogen gas was introduced into the autoclaveunder pressure to a pressure of 40 kg/cm² G and thereafter thetemperature was raised up to 70° C. The reaction was continued at thattemperature for 55 minutes. The absorption of hydrogen gas did not takeplace any more at the time when the total amount of hydrogen gasabsorbed reached about 16.5 Nl and, therefore, the reaction was stopped.The reaction mixture was cooled to room temperature, removed from theautoclave and filtered. Vacuum distillation was carried out at apressure of 5 to 6 mmHg to obtain 23.9 g (yield 88.0%) of a distillatehaving a distillation range of 120° to 122° C.

The resulting liquid was colorless and clear and was identified to beα-(3-aminophenyl)ethylamine in terms of elemental analysis, GC-MCspectra, IR spectra, ¹ H-NMR spectra. The results thus observed arelisted below. In addition, the purity thereof as determined by gaschromatography was found to be 99.3%.

(1) ¹ H-NMR spectra (100 MHz, DMSO-d₆): δppm: ##STR21##

(2) IR Spectra (rock salt plate; neat): cm⁻¹ : 3400, 3340, 3190, 2940,1600, 1485, 1455, 1360, 1310, 1160

(2) GC-MC Spectra: EI-MS Spectrum: (M⁺)=136; (Note: Molecular weight ofAPEA (C₈ H₁₂ N₂)=136.2)

(4) Elemental Analysis (for C₈ H₁₂ N₂)

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             70.48        8.81   20.56                                        Found (%)    70.45        8.91   20.38                                        ______________________________________                                    

EXAMPLE 3 Preparation of α-(3-aminocyclohexyl)methylamine

The same procedures used in Example 1 were repeated except that 45.2 g(0.37 mole) of 3-aminobenzylamine was substituted for 3-APEA used inExample 1. After the reaction, the catalyst was removed and the waterwas removed from the reaction solution by distillation in vacuo. Thendistillation was further performed at a pressure of 3 to 6 mmHg toobtain 41.5 g (yield 87%) of a distillate having a distillation range offrom 80° to 90° C. This liquid was colorless and transparent and thepurity of the product as measured by gas chromatography was found to be99.3%. The result on elemental analysis is as follows:

Elemental Analysis (for C₇ H₆ N₂):

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             65.52        12.48  21.84                                        Found (%)    65.43        12.51  21.71                                        ______________________________________                                    

EXAMPLE 4 Preparation of α-(3-aminocyclohexyl)propylamine

The same procedures used in Example 1 were repeated except that 55.5 g(0.37 mole) of α-(3-aminophenyl)propylamine was substituted for 3-APEAused in Example 1. After the reaction, the catalyst was removed and thewater was removed from the reaction solution by distillation in vacuo.Then distillation was further performed at a pressure of 3 to 6 mmHg toobtain 49.0 g (yield 85%) of a distillate having a distillation range offrom 85° to 95° C. This liquid was colorless and transparent and thepurity of the product as measured by gas chromatography was found to be99.2%. The result on elemental analysis is as follows:

Elemental Analysis (for C₉ H₂₀ N₂):

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             69.14        12.80  17.93                                        Found (%)    69.00        12.85  17.81                                        ______________________________________                                    

EXAMPLE 5 Preparation of α-(aminocyclohexyl)ethylamine

The same procedures used in Example 1 were repeated except that 50.2 g(0.37 mole) of an APEA mixture which comprised 8.5 mole % of 2-isomer,48.8 mole % of 3-isomer and 42.7 mole % of 4-isomer was substituted for3-APEA used in Example 1. The resulting α-(aminocyclohexyl)ethylaminewas analyzed by gas chromatography and found that it comprised 5.5 mole% of 2-isomer, 51.3 mole % of 3-isomer and 43.2 mole % of 4-isomer.After the reaction, the catalyst was removed and the water was removedfrom the reaction solution by distillation in vacuo. Then distillationwas further performed at a pressure of 3 to 6 mmHg to obtain 43.1 g(yield 82.2%) of a distillate having a distillation range of from 83° to93° C.

EXAMPLE 6 Preparation of α-(aminocyclohexyl)butylamine

The same procedures used in Example 5 were repeated except that 60.7 g(0.37 mole) of an α-(aminophenyl)butylamine mixture which comprised 7.1mole % of 2-isomer, 53.9 mole % of 3-isomer and 39.0 mole % of a-isomerwas substituted for the APEA mixture used in Example 5 to obtain 50.7 g(yield 80.5%) of an α-(aminocyclohexyl)butylamine mixture.

EXAMPLE 7 Preparation of α-(isocyanatocyclohexyl)ethylisocyanate(hereunder referred to as "IECI")

To a 2 l reaction flask equipped with a stirring machine, a thermometer,a tube for introducing phosgene gas, a condenser and a dropping funnel,there was introduced 660 g of anhydrous toluene, the internaltemperature of the flask was maintained at about 2° C. by immersing theflask in an ice-water bath with stirring and phosgene gas was introducedinto the flask at a rate of 50 g/h over 90 minutes. Then a solution of29.5 g (0.208 mole) of α-(3-aminocyclohexyl) ethylamine (ACEA) in 300 gof anhydrous toluene was dropwise added to the flask over 80 minutes.During the dropwise addition of the solution of ACEA in anhydroustoluene, cold phosgenation was performed at a temperature of 1° to 5° C.with the introduction of phosgene at a rate of 50 g/h and aftercompletion of the dropwise addition, phosgene was further introduced at5° to 7° C. at a rate of 50 g/h for additional 40 minutes.

After the dropwise addition of the ACEA-anhydrous toluene solution, apale yellowish white slurry was formed in the flask. Then thetemperature of the liquid in the flask was raised up to 86° C. over 2hours while phosgene was introduced into the flask at a rate of 25 g/h.After raising the temperature, hot phosgenation was carried out at atemperature ranging from 86° to 108° C. for 6 hours while continuouslyintroducing phosgene at a rate of 25 g/h. During the hot phosgenation,the liquid in the flask became a pale brown clear solution. The totalamount of phosgene introduced during the cold-hot two-stage phosgenationwas 375 g. This corresponds to 9.1 times the stoichiometric amount.Excess phosgene gas can be recovered by solvent-absorption. After thehot phosgenation, nitrogen gas was introduced into the reaction solutionat a temperature of 103° to 104° C. at a flow rate of 650 ml/min for 2hours 20 minutes to perform degassing.

After cooling the solution, the solvent, toluene, was removed bydistillation under reduced pressure to thus obtain about 37 g of a brownreaction solution. The resultant solution was further purified bydistillation under reduced pressure to thus recover about 30.3 g of adistillate having a boiling point of 139° C./7 mmHg (colorlesstransparent liquid; NCO content=43.2%). The result on elemental analysisof this distillate is as follows:

Elemental Analysis (for C₁₀ H₁₄ N₂ O₂):

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             61.8         7.2    14.4                                         Found (%)    61.6         7.0    14.2                                         ______________________________________                                    

Moreover, in GC-MS spectrometry, it was found that (M⁺) was 194 whichwas well consistent with the molecular weight of the compoundrepresented by C₁₀ H₁₄ N₁ O₂. On the basis of the foregoing facts, thedistillate was identified to beα-(3-isocyanatocyclohexyl)ethylisocyanate.

The resulting α-(3-isocyanatocyclohexyl)ethylisocyanate was a mixture ofits trans- and cis-isomers and ratio of the amount of the trans-isomerto that of the cis-isomer was found to be 10:3 in terms of ¹ H-NMRspectroscopy measurement.

EXAMPLE 8 Preparation of IECI

To the same 2 l reaction flask used in Example 7, there was introduced870 g of butyl acetate, the internal temperature of the flask wasmaintained at about 2° C. by immersing the flask in an ice-water bathwith stirring and phosgene gas was introduced into the flask at a rateof 65 g/h over one hours. Then a solution of 41.5 g (0.292 mole) of ACEAin 374 g of butyl acetate was dropwise added to the flask over 105minutes. During the dropwise addition of the solution of ACEA in butylacetate, cold phosgenation was performed at a temperature of 3° to 8° C.with the introduction of phosgene at a rate of 57 g/h and aftercompletion of the dropwise addition, phosgene was further introduced at8° to 11° C. at a rate of 50 g/h over 15 minutes.

After the dropwise addition of the ACEA-butyl acetate solution, a paleyellowish white slurry was formed in the flask. Then the temperature ofthe liquid in the flask was raised up to 86° C. over 130 minutes whilephosgene was introduced into the flask at a rate of 25 g/h. Afterraising the temperature, hot phosgenation was carried out at atemperature ranging from 86° to 120° C. for 8 hours 40 minutes whilecontinuously introducing phosgene at a rate of 25 g/h. During the hotphosgenation, the liquid in the flask became an almost clear solution,but a small amount of insoluble matter remained. Thus, nitrogen gas wasblown through the solution at 120° C. for 2 hours, after the hotphosgenation, to perform degassing, the solution was cooled and thenfiltered to remove the insoluble matter. The solvent, butyl acetate, wasremoved from the solution, from which the insoluble matter was removed,by distillation under reduced pressure to thus obtain about 50 g of abrown reaction solution. The resultant solution was further purified bydistillation under reduced pressure to thus recover about 43.0 g of adistillate having a boiling point of 142° C./8 mmHg (colorlesstransparent liquid; NCO content=43.2%). The result on elemental analysisof this distillate is as follows:

Elemental Analysis:

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             61.7         7.0    14.3                                         Found (%)    61.8         7.2    14.4                                         ______________________________________                                    

IR spectra and ¹ H-NMR spectra: The same results observed in Example 7were obtained.

EXAMPLE 9 Preparation of IECI

In this Example, phosgenation was performed according to a hydrochlorideprocess. o-Dichlorobenzene was used as a solvent. A solution of 42.7 g(0.30 mole) of ACEA in 1,150 g of o-dichlorobenzene was introduced intothe same 2 l reaction flask used in Example 7 and cooled to 18° C. withstirring. Then hydrogen chloride gas was bubbled into the solution toform hydrochlorides. As the hydrochloride was formed, the temperature ofthe solution was raised and correspondingly the solution was cooled sothat the temperature was maintained at not higher than 35° C. After 90minutes, the introduction of hydrogen chloride gas was stopped, and thetemperature of the resulting hydrochloride slurry was raised to 125° C.over 90 minutes while blowing phosgene gas into the slurry at a rate of50 g/h. Further, phosgene gas was introduced at a rate of 50 g/h at thattemperature for 9 hours. At this stage, the reaction solution becamealmost clear and thus the introduction of phosgene was stopped andnitrogen gas was bubbled into the solution at 125° C. for 2 hours toperform degassing. After cooling the reaction solution which had beendegassed was filtered to remove a small amount of insoluble matter andthen the solvent, o-dichlorobenzene, was removed by distillation underreduced pressure to thus recover about 54 g of a brown liquid. Theliquid was further purified by distillation under reduced pressure toobtain about 45.6 g of a distillate having a boiling point of 142° C./8mmHg (colorless transparent liquid; NCO content=43.1%). The results onthe measurements of IR spectra and ¹ H-NMR spectra as well as elementalanalysis were almost consistent with those for the product in Example 7.

EXAMPLE 10 Preparation of α-(3-isocyanatocyclohexyl)methylisocyanate

In this Example, phosgenation was likewise performed according to ahydrochloride process. Amyl acetate was used as a solvent. 460 g of amylacetate was introduced into a 1 l reaction flask and hydrogen chloridegas was introduced into the amyl acetate at a rate of 36 g/h for about45 minutes while cooling the flask to a temperature of about 0° to 5° C.by immersing it in an ice-water bath with stirring. Then a solution of32.1 g (0.25 mole) of α-(3-aminocyclohexyl) methylamine in 303 g of amylacetate was dropwise added to the solution over 90 minutes. During thedropwise addition, the temperature of the contents was maintained at 5°to 12° C. while introducing hydrogen chloride gas at a rate of 30 g/h tothus form hydrochlorides. After the dropwise addition of the aminesolution, hydrogen chloride gas was bubbled into the solution at a rateof 30 g/h for additional 30 minutes. At this stage, the introduction ofhydrogen chloride gas was stopped, and the temperature of the resultinghydrochloride slurry was raised to 110° C. over about 60 minutes whileblowing phosgene gas into the slurry at a rate of 50 g/h. Further,phosgenation reaction was continued by introducing phosgene at a rate of50 g/h at a temperature of 110° to 125° C. for 2 hours and at atemperature of 125° to 137° C. for 3.5 hours. At this stage, thereaction solution became almost clear and thus the introduction ofphosgene was stopped and nitrogen gas was bubbled into the solution at136° C. for 2 hours to perform degassing. After cooling the reactionsolution which had been degassed, it was filtered to remove a smallamount of insoluble matter and then the solvent, amyl acetate, wasremoved by distillation under reduced pressure to thus recover about 45g of a brown liquid. The liquid was further purified by distillationunder reduced pressure (1 to 2 mmHg) to obtain about 38 g of adistillate having a distillation range of 112° to 115° C. (colorlesstransparent liquid; NCO content=46.55%). The purity of this distillateas determined by gas chromatography was found to be 99. 51%. The resulton elemental analysis is given below. Elemental Analysis (for C₉ H₁₂ N₂O₂):

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             59.93        6.66   15.54                                        Found (%)    59.81        6.70   15.40                                        ______________________________________                                    

EXAMPLE 11 Preparation of α-(3-isocyanatocyclohexyl)propylisocyanate

The same procedures used in Example 10 were repeated except that 39.1 g(0.25 mole) of α-(3-aminocyclohexyl)propylamine was substituted for 32.1g of α-(3-aminocyclohexyl)methylamine used in Example 10 to obtain about29 g of a brown reaction liquid. The liquid was further purified bydistillation under reduced pressure (1 to 2 mmHg) to thus recover 44.7 gof a distillate having a distillation range of from 116° to 120° C.(colorless transparent liquid; content of NCO=40.3%).

The purity of this distillate as determined by gas chromatography wasfound to be 99.7%. The result on elemental analysis is given below.

Elemental Analysis (for C₁₁ H₁₆ N₂ O₂):

    ______________________________________                                                   C          H      N                                                ______________________________________                                        Calculated (%)                                                                             63.40        7.68   13.45                                        Found (%)    63.20        7.70   13.40                                        ______________________________________                                    

EXAMPLE 12 Preparation of3-(α-isocyanatocyclohexyl)ethylisocyanatoisocyanurate (hereunderreferred to as "IECI-isocyanurate")

(1) Preparation of a mixture of catalyst or the like (catalyst B)

The following catalyst and the like were prepared.

    ______________________________________                                        Trimerization catalyst:                                                       Potassium acetate 2.0 g   (2.56 × 10.sup.-2 mole)                       Potassium cyanate 0.4 g   (0.65 × 10.sup.-2 mole)                       Co-catalyst:                                                                  Polyethylene glycol #400                                                                        18.0 g  (4.5 × 10.sup.-2 mole)                        (MW = 400)                                                                    Stabilizer:                                                                   2,6-Di-t-butyl-4-methylphenol                                                                   0.2 g   (9.62 × 10.sup.-4 mole)                       Triphenyl phosphite                                                                             0.2 g   (6.45 × 10.sup.-4 mole)                       Solvent:                                                                      Butyl acetate     20.0 g                                                      Total             40.8 g                                                      ______________________________________                                    

(2) Preparation of Stopping agent C

This was prepared by dissolving 0.5 g (as H₃ PO₄ ; 5.1×10⁻³ mole) in 25g of butyl acetate.

(3) Preparation of IECI-isocyanurate

To a 30 ml four-necked flask, there were added 10.0 g of IECI (obtainedby phosgenation of α-(3-aminocyclohexyl)ethylamine) and 3.3 g of butylacetate as a solvent to dissove the former in the latter and thetemperature was adjusted to 25° C. with stirring in a nitrogen gasblanket. 0.4 g of the catalyst B prepared above was added thereto, thenthe flask was externally warmed to control the temperature of thesolution to 70° C.

When the amount of unreacted free IECI was determined by gaschromatography on each sample of the reaction solution collectedperiodically, 8 hours after the addition of the catalyst B, the amountof free IECI was reduced to about 37%. At this stage, 0.75 g of thestopping agent C was added to the reaction system, stirring wascontinued for additional one hour and then the stirring was stopped toremove the contents of the flask.

The weight of the contents removed was 14.0 g.

After removing excess IECI and the solvent by distillation under reducedpressure, 5.1 g of the resulting pale yellowish white solids were againdissolved in 5.1 g of butyl acetate.

The composition of this solution was as follows:

    ______________________________________                                        Solid contents (non-volatile matter)                                                                50.0%   by weight                                       NCO content           9.1%    by weight                                       Free IECI             0.8%    by weight                                       Chlorine capable of causing hydrolysis                                                              0.011%  by weight                                       ______________________________________                                    

The product was reacted with methyl alcohol to form a methylcarbamatecompound thereof and the methylcarbamate compound was analyzed by GPC.As a result, it is found that the product comprised the followingoligomers in amounts described below:

    ______________________________________                                        n = 1 (trimer)   43.8%                                                        n = 2 (pentamer) 20.6%                                                        n = 3 (heptamer) 13.2%                                                        n = 4 and 5      22.4%                                                        ______________________________________                                    

FIG. 4 shows the result of IR spectrometric measurement of this product(rock salt plate: (50% by weight) solution: control solution: a butylacetate solution).

Absorptions observed at 1400 to 1420 cm⁻¹ and 1690 to 1700cm⁻¹ are theabsorption bands due to the isocyanurate ring and that observed at 2220to 2230cm⁻¹ is the absorption band due to the presence of the isocyanatogroup.

EXAMPLE 13

To a flask similar to that used in Example 12, there were added 20.0 gof IECI and 6.6 g of butyl acetate and the mixture was stirred in anitrogen gas blanket to control the temperature to 25° C.

To the solution, there was added 0.6 g of a catalyst B (prepared in thesame manner as in Example 12), then the flask was externally warmed tocontrol the temperature of the solution to 60° C. When the amount ofunreacted free IECI was determined by gas chromatography on each sampleof the reaction solution collected periodically, 12 hours after theaddition of the catalyst B, the amount of free IECI was reduced to about34%. At this stage, 1.1 g of a stopping agent C (prepared in the samemanner as in Example 12) was added to the reaction system, stirring wascontinued for additional one hour at a temperature of 50° C. and thenthe stirring was stopped to remove the contents of the flask.

The weight of the contents removed was 26.0 g.

After removing excess IECI and the solvent by distillation under reducedpressure, 10.7 g of the resulting pale yellowish white solids were againdissolved in 10.7 g of butyl acetate.

The composition of this solution was as follows:

    ______________________________________                                        Solid contents (non-volatile matter)                                                               50.0%    by weight                                       NCO content          9.2%     by weight                                       Free IECI            1.0%     by weight                                       ______________________________________                                    

The product was reacted with methyl alcohol to form a methylcarbamatecompound thereof and the methylcarbamate compound was analyzed by GPC.As a result, it is found that the product comprised the followingoligomers in amounts described below:

    ______________________________________                                        n = 1 (trimer)         39.0%                                                  n = 2 (pentamer)       23.1%                                                  n = 3 to 5             37.9%                                                  ______________________________________                                    

EXAMPLE 14 Preparation of [(3-isocyanatocyclohexyl)methylisocyanate]-isocyanurate (hereunder referred to as"ICMI-isocyanurate")

To a flask similar to that used in Example 12, there were added 10.0 g(0.056 mole) of (3-isocyanatocyclohexyl)methylisocyanate (prepared byphosgenating (3-aminocyclohexyl)methylamine; hereinafter referred to as"ICMI") and 3.3 g of butyl acetate and the temperature was adjusted to25° C. with stirring in a nitrogen gas blanket. 0.4 g (0.00031 mole) ofa catalyst B (prepared in the same manner as in Example 12) was addedthereto, then the flask was externally warmed or cooled to control thetemperature of the solution to 70° C.

When the amount of unreacted free ICMI was determined by gaschromatography on each sample of the reaction solution collectedperiodically, 6 hours after the addition of the catalyst B, the amountof free ICMI was reduced to not higher than 35%. At this stage, 0.75 g(0.00015 mole) of a stopping agent C (prepared in the same manner as inExample 12) was added to the reaction system, stirring was continued foradditional one hour at a temperature of 60° C. and then the stirring wasstopped to remove the contents of the flask.

The weight of the contents removed was 10.1 g.

After removing excess ICMI and the solvent by distillation under reducedpressure, 4.8 g of the resulting pale yellowish white solids were againdissolved in 4.8 g of butyl acetate.

The composition of this solution was as follows:

    ______________________________________                                        Solid contents (non-volatile matter)                                                               50.0%    by weight                                       NCO content          10.1%    by weight                                       Free IECI            1.1%     by weight                                       Chlorine capable of causing hydrolysis                                                             0.01%    by weight                                       ______________________________________                                    

The product was reacted with methyl alcohol to form a methylcarbamatecompound thereof and the methylcarbamate compound was analyzed by GPC,As a result, it is found that the product comprised the followingoligomers in amounts described below:

    ______________________________________                                        n = 1 (trimer)         55.4%                                                  n = 2 (pentamer)       21.4%                                                  n = 3 (heptamer)        9.7%                                                  n = 4 and 5            12.3%                                                  ______________________________________                                    

EXAMPLE 15 Preparation of [(3(4)-isocyanatocyclohexyl)methylisocyanate]-isocyanurate

To a flask similar to that used in Example 12, there were added 10.0 g(0.056 mole) of a mixture of (3-isocyanatocyclohexyl) methylisocyanateand (4-isocyanatocyclohexyl)methylisocyanate (obtained by phosgenationof a mixture of (3-aminocyclohexyl) methylamine and(4-aminocyclohexyl)methylamine; hereunder referred to as "ICMI") and 3.3g of butyl acetate to dissolve the former in the latter and thetemperature was adjusted to 25° C. with stirring in a nitrogen gasblanket. 0.4 g (3.2×10⁻⁴ mole) of a catalyst B (prepared in the samemanner as in Example 12) was added thereto, then the flask wasexternally warmed or cooled to control the temperature of the solutionto 60° C.

When the amount of unreacted free ICMI was determined by gaschromatography on each sample of the reaction solution collectedperiodically, 12 hours after the addition of the catalyst B, the amountof free ICMI was reduced to not higher than 35%. At this stage, 0.75 g(8.83×10⁻⁵ mole) of a stopping agent C (prepared in the same manner asin Example 12) was added to the reaction system, stirring was continuedfor additional one hour at 60° C. and then the stirring was stopped toremove the contents of the flask. The weight of the contents removed was10.1 g. After removing excess ICMI and the solvent by distillation underreduced pressure, 4.9 g of the resulting pale yellowish white solidswere again dissolved in 4.9 g of butyl acetate. The composition of thissolution was as follows:

    ______________________________________                                        Solid contents (non-volatile matter)                                                                50.0%   by weight                                       NCO content           10.3%   by weight                                       Free IECI             1.1%    by weight                                       Chlorine capable of causing hydrolysis                                                              0.009%  by weight                                       ______________________________________                                    

The product was reacted with methyl alcohol to form a methylcarbamatecompound thereof and the methylcarbamate compound was analyzed by GPC.As a result, it is found that the product comprised the followingoligomers in amounts described below:

    ______________________________________                                        n = 1 (trimer)   60.3%                                                        n = 2 (pentamer) 22.0%                                                        n = 3 (heptamer) 10.5%                                                        n = 4 and 5       7.2%                                                        ______________________________________                                    

REFERENCE EXAMPLE 2 (Preparation of Acryl Polyol Resin)

A mixed monomer liquid which comprised 150 g of 2-hydroxyethylmethacrylate, 50 g of methyl methacrylate, 150 g of n-butylmethacrylate, 25 g of n-butyl acrylate, 125 g of styrene, 15 g ofacrylic acid, 25 g of diethylene glycol and 50 g oft-butylperoxy-2-ethylhexanoate was dropwise added continuously, over 2hours, to 1,200 g of n-butyl acetate which had been refluxed, and thereflux was continued for additional 5 hours to polymerize the monomers.After completion of the polymerization reaction, a part of the n-butylacetate was distilled off to adjust the concentration of the solidcontent to 80%. The acryl polyol solution thus prepared had a viscosityof 6,500 cp/25° C., a number average molecular weight of 1,300 and ahydroxyl value of 92 KOH mg/g.

REFERENCE EXAMPLE 3 (Preparation of Base Enamel)

Base enemal was prepared by compounding the acryl polyol solutionprepared in Reference Example 2 as described below.

    ______________________________________                                        The acryl polyol prepared in Reference Example 2                                                          45 g                                              Pigment: Titanium oxide R930 (available from                                                              45 g                                              Ishihara Sangyo Co.                                                           Thinner (a mixed solution of xylene/toluene/butyl                                                         10 g                                              acetate/methyl ethyl ketone)                                                  ______________________________________                                    

The above components were blended in the proportion listed above and thepigment was kneaded into the blend with a three-roll mill to obtain anintended base enamel.

EXAMPLES 16 TO 18 AND COMPARATIVE EXAMPLES 3 TO 6

Compositions for forming urethane resins according to the presentinvention was prepared by compounding each of solutions of isocyanuratetype polisocyanates obtained in Examples 12, 14 and 15, the acryl polyolresin solution as shown in Reference Example 2 and the base enamelprepared in Reference Example 3 so that the molar amount of theisocyanato group was equal to that of the hydroxyl group and the contentof pigments (PWC) was 40% by weight; adding a thinner comprising ethylacetate/toluene/butyl acetate/xylene/cellosolve acetate (weightratio=30/30/20/15/5) and then adjusting to 15 sec./25° C. with Ford-Cup#4.

The resulting composition was coated on the surface of steel plates andglass plates with an air spray gun (IWATANI-77 Model; nozzle diameter 2mm φ) so that the thickness of the film determined after drying was 25μ,allowed to stand at room temperature (20° C/60%RH) for 7 days and wasused in the following tests.

For comparison, the same tests were also carried out using conventionalsamples, i.e., an organic polyisocyanate derived from tolylenediisocyanate (OLESTER P75 availavle from MITSUI TOATSU CHEMICALS, INC.)and three kinds of aliphatic polyisocyanates: (1) OLESTER NP1000(availavle from MITSUI TOATSU CHEMICALS, INC.); (2) CORONATE EH (anisocyanurate derivative of hexamethylene diisocyanate available fromNIPPON POLYURETHANE CO., LTD.); and (3) IPDI T1890 (DAICEL . HUELS Co.,Ltd.). Coated film performance and physical properties of these samplesare listed in the following Table 1.

The tests on the properties of the coated films were performed at 20°C./60%RH and they were evaluated according to JIS K-5400. In Table 1, 1)to 9) are as follows:

1) Adhesion: determined according to JIS D-0202.

2) Erichsen extrusion: determined according to JIS Z-2247.

3) Magic staining properties: determined according to JAS 1373. Morespecifically, a test piece is horizontally placed, a line of 10 mm widewas drawn on the surface of the test piece with a quick-drying inkdefined in JIS S-6037(1964), allowed to stand for 24 hours and thenwiped off with a cloth containing an alcohol. The results are estimatedaccording to the following three stage evaluation standard.

◯: there remains no mark; Δ: there remains slight mark; ×: there remainsclear mark.

4) Xylene rubbing (50 times): A test piece was fixed on a tester forfastness to rubbing of dyed materials and cotton cloth containing 2 mlof xylene was moved back and forth for 50 times under a load of 500 g.The result is estimated according to the following three stageevaluation:

◯: no abnormality; Δ: there remains slight rubbing mark; ×: the surfaceof the substrate can be seen.

5) Resistance to acids and alkalis: determined according to JAS 1373.More specifically, a test piece is horizontally placed, a 10% aqueoussulfuric acid solution (or a 10% aqueous sodium hydroxide solution) isdropwise added to the surface of the test piece, the surface is coveredwith a watch glass for 24 hours and then allowed to stand for 24 hours.The result is estimated according to the following three stageevaluation:

◯: no abnormality; Δ: there remains slight mark; ×: there remains clearmark.

6) WOM degree of yellowing: determined according to JIS K-7103.

7) Gloss (60° gloss): determined according to JIS K-5400.

8) Du-Pont impact (1/2 in/500 g): determined according to JIS K-5400.

9) Secondary Physical properties: After a sample is immersed in boilingwater for 4 hours, physical properties are determined.

EXAMPLE 19 AND COMPARATIVE EXAMPLES 7 TO 10

The same tests as those in Example 16 were performed on a typicalcommercially available acryl polyol resin, i.e., OLESTER Q182 (MITSUITOATSU CHEMICALS. INC.; number average molecular weight=9,500; contentof solids=50%; hydroxyl value=45 KOHmg/g). The same procedures used inExample 16 were repeated except that a different compound having activehydrogen atoms was employed.

On the other hand, the same tests were performed on the four kinds ofthe aliphatic polyisocyanates used in Comparative Examples 3 to 6. Theresults obtained are summarized in the following Table 2.

Tests on quality of coated films and methods for evaluation were thesame as those employed in Example 16.

EXAMPLE 20 AND COMPARATIVE EXAMPLES 11 TO 14

The same tests as those in Example 16 were performed on a commerciallyavailable polyester polyol resin, i.e., OLESTER Q 173 (MITSUI TOATSUCHEMICALS. INC.; content of solids=100%; hydroxyl value=256 KOHmg/g).The same procedures used in Example 16 were repeated except that adifferent compound having active hydrogen atoms was employed.

On the other hand, the same tests were performed on the four kinds ofthe aliphatic polyisocyanates used in Comparative Examples 3 to 6. Theresults obtained are summarized in the following Table 3.

Tests on quality of coated films and methods for evaluation were thesame as those employed in Example 16.

EXAMPLE 21

The same tests used in Example 19 were performed on a sample which hadthe same composition as that used in Example 16 except that an organicpolyisocyanate component used was a solution of the isocyanurate typepolyisocyanate solution obtained in Example 12 to which commerciallyavailable OLESTER NP 1000 (1/1 weight ratio) was added. The resultsobtained are listed in the following Table 2.

Tests on quality of coated films and methods for evaluation were thesame as those employed in Example 16.

EXAMPLE 22

The same tests used in Example 19 were performed on a sample which hadthe same composition as that used in Example 16 except that an organicpolyisocyanate component used was a solution of the isocyanurate typepolyisocyanate solution obtained in Example 12 to which commerciallyavailable OLESTER NP 1000 (1/5 weight ratio) was added. The resultsobtained are listed in the following Table 2.

Tests on quality of coated films and methods for evaluation were thesame as those employed in Example 16.

                                      TABLE 1                                     __________________________________________________________________________                   Example 16                                                                          Example 17                                                                          Example 18                                                                          Comp. Ex. 3                                                                          Comp. Ex. 4                                                                          Comp. Ex.                                                                             Comp. Ex.              __________________________________________________________________________                                                           6                      Compunding                                                                    Isocyanate     Example 12                                                                          Example 14                                                                          Example 15                                                                          OLESTER                                                                              CORONATE                                                                             IPDI T = 1890                                                                         OLESTER P75                                             NP1000 EH                                    Active H-containing compound                                                                 Acryl polyol of Reference Example 2 and base enamel of                        reference Example 3                                            Compatibility  good  good  good  good   good   good    good                   Reactivity                                                                    Set to touch (min.)                                                                          10    9     9     13     13     15      8                      Complete hardening (min.)                                                                    225   220   220   300    300    270     100                    Pot life (hr.) ≧24                                                                          ≧24                                                                          ≧24                                                                          ≧24                                                                           ≧24                                                                           ≧24                                                                            20                     Film appearance                                                                              good  good  good  good   good   good    good                   Film thickness (μ)                                                                        22.7  23.4  24.7  24.3   23.8   24.1    25.4                   Gloss (60° gloss) 7)                                                                  92    92    93    92     89     88      85                     Erichsen extrusion (cm) 2)                                                                   ≧8                                                                           ≧8                                                                           ≧8                                                                           ≧8                                                                            ≧8                                                                            7.29    3.27                   DuPont impact (1/2 in/500 g) 8)                                                              ≧50                                                                          ≧50                                                                          ≧50                                                                          ≧50                                                                           ≧50                                                                           ≧50                                                                            25                     Magic ink staining 3)                                                         (Red)          ∘                                                                       ∘                                                                       ∘                                                                       .increment.                                                                          ∘                                                                        ∘                                                                         ∘          (Black)        ∘                                                                       ∘                                                                       ∘                                                                       .increment.                                                                          .increment.                                                                          .increment.                                                                           ∘          (Blue)         ∘                                                                       ∘                                                                       ∘                                                                       .increment.                                                                          ∘                                                                        X       ∘          Xylene rubbing (50 times) 4)                                                                 ∘                                                                       ∘                                                                       ∘                                                                       .increment.                                                                          .increment.                                                                          .increment.                                                                           ∘          Adhesion 1)    100/100                                                                             100/100                                                                             100/100                                                                             100/100                                                                              100/100                                                                              100/100 50/100                 Pencil hardness                                                                              H     H     H     F      H      H       H                      Resistance to acid 5)                                                                        ∘                                                                       ∘                                                                       ∘                                                                       ∘                                                                        ∘                                                                        ∘                                                                         ∘          Resistance to alkali 5)                                                                      ∘                                                                       ∘                                                                       ∘                                                                       ∘                                                                        ∘                                                                        ∘                                                                         ∘          Secondary physical properties                                                 Appearance     no change                                                                           no change                                                                           no change                                                                           no change                                                                            no change                                                                            no change                                                                             no change              Gloss (60° gloss) 7)                                                                  90    90    90    89     88     85      82                     Erichsen extrusion (cm) 2)                                                                   1.02  1.21  1.53  5.35   4.76   0.53    0.28                   DuPont impact (1/2 in/500 g) 8)                                                              30    30    30    45     40     20      10                     Adhesion 1)    100/100                                                                             100/100                                                                             100/100                                                                             100/100                                                                              100/100                                                                              100/100 0/100                  WOM degree of yellowing                                                       (.increment.E) 6)                                                              200 hrs.      0.48  0.52  0.51  0.45   0.42   0.52    3.62                    500 hrs.      0.84  0.92  0.91  0.85   0.73   0.91    4.53                   1000 hrs.      1.53  1.73  1.81  2.13   1.69   2.02    5.68                   __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________                Example 19                                                                          Comp. Ex. 7                                                                          Comp. Ex. 8                                                                          Comp. Ex. 9                                                                          Comp. Ex. 10                                                                          Example 21                                                                            Example                __________________________________________________________________________                                                           22                     Compunding                                                                    Isocyanate  Example 12                                                                          OLESTER                                                                              CORONATE                                                                             IPDI T =                                                                             OLESTER P75                                                                           Ex. 12/ Ex. 12/                                  NP1000 EH     1890           OLESTER OLESTER                                                               NP1000 = 1/1                                                                          NP1000 = 1/5           Content of IECI                                                                           100   0      0      0      0       40      12                     isocyanurate type poly-                                                       isocyanate in the total                                                       amount of organic                                                             polyisocyanate (wt %)                                                         Active H-containing                                                                       OLESTER Q182                                                      compound                                                                      Compatibility                                                                             good  good   good   good   good    good    good                   Reactivity                                                                    Set to touch (min.)                                                                       8     21     19     17     7       15      19                     Complete hardening                                                                        47    60     58     56     30      50      57                     (min.)                                                                        Pot life (hr.)                                                                            ≧24                                                                          ≧24                                                                           ≧24                                                                           ≧24                                                                           10      ≧24                                                                            ≧24             Film appearance                                                                           good  good   good   good   good    good    good                   Film thickness (μ)                                                                     22.0  21.7   23.0   22.5   23.5    23.0    22.7                   Gloss (60° gloss) 7)                                                               93.7  88.2   84.4   85.0   83.2    90.7    85.3                   Erichsen extrusion                                                                        2.51  7.45   7.67   0.10   0.12    4.27    6.23                   (cm) 2)                                                                       DuPont impact                                                                             20    30     15     15     10      20      30                     (1/2 in/500 g) 8)                                                             Magic ink staining 3)                                                         (Red)       ∘                                                                       .increment.                                                                          ∘                                                                        X      ∘                                                                         ∘                                                                         .increment.            (Black)     ∘                                                                       X      .increment.                                                                          X      ∘                                                                         .increment.                                                                           X                      (Blue)      ∘                                                                       X      .increment.                                                                          X      ∘                                                                         ∘                                                                         .increment.            Xylene rubbing                                                                            ∘                                                                       .increment.                                                                          .increment.                                                                          X      ∘                                                                         ∘                                                                         .increment.            (50 times) 4)                                                                 Adhesion 1) 100/100                                                                             100/100                                                                              100/100                                                                              100/100                                                                              100/100 100/100 100/100                Pencil hardness                                                                           2 H   H      2 H    H      2 H     2 H     H                      Resistance to acid 5)                                                                     ∘                                                                       ∘                                                                        ∘                                                                        ∘                                                                        ∘                                                                         ∘                                                                         ∘          Resistance to alkali 5)                                                                   ∘                                                                       ∘                                                                        ∘                                                                        ∘                                                                        ∘                                                                         ∘                                                                         ∘          Secondary physical                                                            properties                                                                    Appearance  no change                                                                           no change                                                                            no change                                                                            no change                                                                            no change                                                                             no change                                                                             no change              Gloss (60° gloss) 7)                                                               88.5  84.0   84.4   84.5   82.2    84.2    84.3                   Erichsen extrusion                                                                        0.51  5.34   6.42   0.12   0.20    2.35    4.20                   (cm) 2)                                                                       DuPont impact                                                                             20    25     25     20     10      20      25                     (1/2 in/500 g) 8)                                                             Adhesion 1) 100/100                                                                             100/100                                                                              100/100                                                                              70/100 0/100   100/100 100/100                WOM degree of                                                                 yellowing (.increment.E) 6)                                                    200 hrs.   0.44  0.35   0.42   0.53   3.82    0.65    0.47                    500 hrs.   0.77  0.78   0.65   0.82   4.57    0.63    0.85                   1000 hrs.   1.56  2.15   1.88   2.25   5.29    1.72    1.94                   __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________                   Example 20                                                                          Comp. Ex. 11                                                                         Comp. Ex. 12                                                                         Comp. Ex. 13                                                                          Comp. Ex. 14                       __________________________________________________________________________    Compunding                                                                    Isocyanate     Example 12                                                                          OLESTER                                                                              CORONATE                                                                             IPDI T = 1890                                                                         OLESTER P75                                             NP1000 EH                                                Active H-containing compound                                                                 OLESSTER Q173                                                  Compatibility  good  good   good   good    good                               Reactivity                                                                    Set to touch (min.)                                                                          60    69     69     78      55                                 Complete hardening (hr.)                                                                     20    24     24     25      9.5                                Pot life (hr.) ≧48                                                                          ≧48                                                                           ≧48                                                                           ≧48                                                                            22                                 Film appearance                                                                              good  good   good   good    good                               Film thickness (μ)                                                                        25.9  26.7   25.2   24.9    25.7                               Gloss (60° gloss) 7)                                                                  98.3  98.9   98.0   98.5    98.3                               Erichsen extrusion (cm) 2)                                                                   ≧8                                                                           ≧8                                                                            ≧8                                                                            ≧8                                                                             ≧8                          DuPont impact (1/2 in/500 g) 8)                                                              ≧50                                                                          ≧50                                                                           ≧50                                                                           ≧50                                                                            ≧50                         Magic ink staining 3)                                                         (Red)          .increment.                                                                         X      X      X       ∘                      (Black)        .increment.                                                                         X      X      X       ∘                      (Blue)         ∘                                                                       X      .increment.                                                                          X       ∘                      Xylene rubbing (50 times) 4)                                                                 .increment.                                                                         X      .increment.                                                                          X       ∘                      Adhesion 1)    100/100                                                                             100/100                                                                              100/100                                                                              100/100 0/100                              Pencil hardness                                                                              F     B      F      B       H                                  Resistance to acid 5)                                                                        ∘                                                                       ∘                                                                        ∘                                                                        ∘                                                                         ∘                      Resistance to alkali 5)                                                                      ∘                                                                       ∘                                                                        ∘                                                                        ∘                                                                         ∘                      Secondary physical properties                                                 Appearance     no change                                                                           no change                                                                            no change                                                                            no change                                                                             no change                          Gloss (60° gloss) 7)                                                                  97.5  97.3   96.2   96.2    97.1                               Erichsen extrusion (cm) 2)                                                                   ≧8                                                                           ≧8                                                                            ≧8                                                                            ≧8                                                                             3.91                               DuPont impact (1/2 in/500 g) 8)                                                              ≧50                                                                          ≧50                                                                           ≧50                                                                           ≧50                                                                            20                                 Adhesion 1)    100/100                                                                             100/100                                                                              100/100                                                                              100/100 0/100                              __________________________________________________________________________

What is claimed is:
 1. A polyisocyanato-isocyanurate represented by thefollowing general formula (IV): ##STR22## wherein R₁, R₂ and R₃ may bethe same or different and each represents a group represented by thefollowing general formula: ##STR23## wherein R represents hydrogen atomor an alkyl group having 1 to 5 carbon atoms and n is an integer rangingfrom 1 to
 5. 2. Polyisocyanato-isocyanurates represented by theforegoing general formula (IV) of claim 1 in which n is 1 and R ishydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. 3.Polyisocyanato-isocyanurates represented by the foregoing generalformula (IV) of claim 1 in which n is an integer ranging from 2 to 5 andR is hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. 4.Polyisocyanato-isocyanurate of claim 1, wherein it comprises 30 to 90%by weight of the polyisocyanato-isocyanurate represented by theforegoing general formula (IV) in which n is 1 and the balance of thepolyisocyanato-isocyanurate of the formula (IV) in which n is an integerranging from 2 to
 5. 5. A method for preparingpolyisocyanato-isocyanurate represented by the foregoing general formula(IV) of claim 1 comprising polymerizing anα-(isocyanatocyclohexyl)alkylisocyanate in the presence of atrimerization catalyst, wherein saidα-(isocyanatocyclohexyl)alkylisocyanate being represented by thefollowing general formula (III): ##STR24## wherein R represents ahydrogen atom or a lower alkyl group having 1 to 5 carbon atoms,provided that the isocyanato group bonded to the cyclohexyl group may bein either of the 2-, 3- and 4-positions, and wherein said trimerizationcatalyst is selected from at least one alkali metal compound of acarboxylic acid, at least one alkali metal compound of cyanic acid, andmixtures thereof.
 6. The method for preparingpolyisocyanato-isocyanurate of claim 5 wherein the trimerizationcatalyst further comprises a polyethylene oxide compound or alcohol. 7.An organic polyisocyanate comprising a polyisocyanato-isocyanuraterepresented by the foregoing general formula (IV) of claim 1 in anamount of not lower than 10% by weight.
 8. A resin comprising an organicpolyisocyanate which comprises not lower than 10% by weight of apolyisocyanato-isocyanurate represented by the foregoing general formula(IV) of claim 1 and a compound having at least two active hydrogen atomsin the molecule.
 9. The resin of claim 8 wherein the equivalent ratio ofthe organic polyisocyanate to the compound having at least two activehydrogen atoms ranges from 0.1:1 to 10:1.
 10. A resin composition forcoating materials comprising the resin as set forth in claim 8.